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Inspector Knowledge Series 04-0

Effect of Alloying Elements on Steels

材料基础-钢材合金元素 图文简易教材

Descriptive approach- Steel Alloys


Mok Chek Min 莫泽民

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Chapter One:
Theory of Strengthening

ƒ The Mechanism of Strengthening.


ƒ Elastic and Plastic Deformation.
ƒ Understanding Dislocation.
ƒ The Nature of Dislocation.
ƒ Crystal Defects.
ƒ Point Defects
ƒ Linear Defects
ƒ Planar Defects.
ƒ Bulk Defects.
ƒ Pinning Overview.
ƒ Methods of Strengthening.
ƒ Works or Strain Hardening.
ƒ Grain Boundary Strengthening.
ƒ Dispersion Strengthening.
ƒ Solid Solution Strengthening.
ƒ Precipitation Hardening.

Chapter Two:
Effects of Alloying Elements on Iron Carbon Alloy

ƒ Introduction
ƒ Characteristics of alloying element
ƒ Brief Summary.

ƒ Carbon. ƒ Lead ƒ Titanium


ƒ Manganese. ƒ Hydrogen ƒ Cobalt
ƒ Nickel. ƒ Selenium
ƒ Chromium. ƒ Tantalum
ƒ Nickel & Chromium ƒ Tin
ƒ Molybdenum. ƒ Calcium
ƒ Vanadium ƒ Cerium
ƒ Tungsten ƒ Nitrogen
ƒ Silicon ƒ Boron
ƒ Copper ƒ Aluminium
ƒ Phosphorous ƒ Zirconium
ƒ Sulphur ƒ Niobium

Appendix D. Page 1 of 116.


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ƒ Carbon contents, steel classification and alloy steels.


ƒ Carbon steels
ƒ Stainless steels
ƒ Strength in steels
ƒ Alloying and its effects on the critical temperature and tensile strength.
ƒ Control of HSLA properties.
ƒ Influence of alloying elements on steel microstructures
ƒ Martensite in austenitic stainless steel welds.
ƒ Alloying effects on martensite, pearlite and bainite formation.
ƒ Steel alloys
ƒ Carbon steels to austenitic steels.
ƒ Selection of age-hardenable superalloys.
ƒ Microplasticity
ƒ More reading.

http://www.arab-eng.org/vb/t93373.html
Introduction to Dislocations, Fourth Edition by Derek Hull, D J Bacon http://mihd.net/lmec67y

Appendix D. Page 2 of 116.


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Chapter One:

The Mechanism of strengthening.

Elastic/Plastic Deformation

When a sufficient load is applied to a metal or other structural material, it will cause the material to change
shape. This change in shape is called deformation. A temporary shape change that is self-reversing after the
force is removed, so that the object returns to its original shape, is called elastic deformation. In other words,
elastic deformation is a change in shape of a material at low stress that is recoverable after the stress is
removed. This type of deformation involves stretching of the bonds, but the atoms do not slip past each other.

When the stress is sufficient to permanently deform


the metal, it is called plastic deformation. As
discussed in the section on crystal defects, plastic
deformation involves the breaking of a limited
number of atomic bonds by the movement of
dislocations. Recall that the force needed to break
the bonds of all the atoms in a crystal plane all at
once is very great. However, the movement of
dislocations allows atoms in crystal planes to slip
past one another at a much lower stress levels.
Since the energy required to move is lowest along
the densest planes of atoms, dislocations have a
preferred direction of travel within a grain of the
material. This results in slip that occurs along
parallel planes within the grain. These parallel slip
planes group together to form slip bands, which can
be seen with an optical microscope. A slip band
appears as a single line under the microscope, but it
is in fact made up of closely spaced parallel slip
planes as shown in the image.

Plastic deformation occurs when large numbers of dislocations move and multiply so as to result in
macroscopic deformation. In other words, it is the movement of dislocations in the material which allows for
deformation. If we want to enhance a material's mechanical properties (i.e. increase the yield and tensile
strength), we simply need to introduce a mechanism which prohibits the mobility of these dislocations.
Whatever the mechanism may be, (work hardening, grain size reduction, etc) they all hinder dislocation motion
and render the material stronger than previously.

Appendix D. Page 3 of 116.


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The stress required to cause dislocation motion is orders of magnitude lower than the theoretical stress
required to shift an entire plane of atoms, so this mode of stress relief is energetically favorable. Hence, the
hardness and strength (both yield and tensile) critically depend on the ease with which dislocations move.
Pinning points, or locations in the crystal that oppose the motion of dislocations, can be introduced into the
lattice to reduce dislocation mobility, thereby increasing mechanical strength.

Dislocations may be pinned due to stress field interactions with other dislocations and solute particles, or
physical barriers from grain boundaries and second phase precipitates. There are several strengthening
mechanisms for metals, however the key concept to remember about strengthening of metallic materials is that
it is all about preventing dislocation motion and propagation; you are making it energetically unfavorable for the
dislocation to move or propagate. For a material that has been strengthened, by some processing method, the
amount of force required to start irreversible (plastic) deformation is greater than it was for the original material.

In amorphous materials such as polymers, amorphous ceramics (glass), and amorphous metals, the lack of
long range order leads to yielding via mechanisms such as brittle fracture, crazing, and shear band formation.
In these systems, strengthening mechanisms do not involve dislocations, but rather consist of modifications to
the chemical structure and processing of the constituent material.

Unfortunately, strength of materials cannot infinitely increase. Each of the mechanisms elaborated below
involves some trade off by which other material properties are compromised in the process of strengthening.

Steel can be strengthened by several basic mechanisms, the most important of which are:

1. Work hardening or strain hardening.


2. Solid solution strengthening by interstitial atoms.
3. Solid solution strengthening by substitutional atoms.
4. Refinement of grain size.
5. Effects of heat treatment on microstructures.
6. Precipitation strengthening.
7. Grain boundary strengthening.
8. Dispersion strengthening, including lamellar and random dispersed structures.

The most distinctive aspect of strengthening of iron and steel is the role of the interstitial solutes carbon and
nitrogen. These elements also play a vital part in interacting with dislocations, and in combining preferentially
with some of the metallic alloying elements used in steels.

Appendix D. Page 4 of 116.


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Understanding dislocations

Introduction to dislocations
http://www.msm.cam.ac.uk/doitpoms/tlplib/dislocations/printall.php

The Nature of Dislocations

Plastid deformation is a measure of material strength, plastic deformation is irreversible. Therefore, the
configuration of the atoms must be changed during plastic deformation, for otherwise they would return to their
original position on unloading. If we consider shearing a single crystal as an example, it can be deformed
plastically by sliding whole layers of atoms against each other as shown in figure above for this sliding to
happen, the bonds between the atoms have to be stretched elastically until they can switch to the next atom.
The stress required for this process can be estimated and is of the order of one fifth of the shear modulus of
the crystal. The yield strength predicted this way for metallic single crystals is thus between 1GPa and 25GPa.
If we measure the strength of single crystals of pure metals, the values found are several orders of magnitudes
below this theoretical value and even lie below that of engineering alloys. Typical values are in the range of a
few mega Pascal. As single crystals always contain lattice defects, one possible explanation could be that
these are responsible for the reduced strength. If, however, the number of defects is reduced further, for
instance by a heat treatment, the yield strength becomes even smaller. Only an absolutely perfect single
crystal without any defects would possess a yield strength agreeing with the theoretical prediction. This can
only be nearly realized in so-called whiskers, which, however, are extremely small. The reason for this
spectacular failure of the theoretical prediction is that plastic deformation does not occur by sliding of complete
layers of atoms. Instead, it proceeds by a mechanism that is based on a special type of lattice defect, the
dislocations. To understand plastic deformation of metals thus requires an understanding of dislocations.

Appendix D. Page 5 of 116.


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Dislocation densities
Dislocation is a lattice imperfection in a crystal structure which exerts a profound effect on a structure sensitive
properties such as strength, hardness, ductility and toughness. There are two types, edge and screw or
combination of both, all of which are characterized by a Burgers vector which represents the amount and
direction of slip when the dislocation moves. Click on the web links provided to read further.

Interaction of Dislocations

Transmission Electron Micrograph of Dislocations Transmission Electron Micrograph of Dislocations

More reading:

http://en.wikipedia.org/wiki/Dislocation
http://www-sgrgroup.materials.ox.ac.uk/lectures/microplasticity.html

Microplasticity: dislocations and strengthening mechanisms

"Atomistics" of edge dislocation motion and Asymmetry of screw and edge dislocation motion in Mo

Appendix D. Page 6 of 116.


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Crystal Defects
A perfect crystal, with every atom of the same type in the correct position, does not exist. All crystals have
some defects. Defects contribute to the mechanical properties of metals. In fact, using the term “defect” is sort
of a misnomer since these features are commonly intentionally used to manipulate the mechanical properties
of a material. Adding alloying elements to a metal is one way of introducing a crystal defect. Nevertheless, the
term “defect” will be used, just keep in mind that crystalline defects are not always bad. There are basic
classes of crystal defects:

ƒ point defects, which are places where an atom is missing or irregularly placed in the lattice structure.
Point defects include lattice vacancies, self-interstitial atoms, substitution impurity atoms, and interstitial
impurity atoms
ƒ linear defects, which are groups of atoms in irregular positions. Linear defects are commonly called
dislocations.
ƒ planar defects, which are interfaces between homogeneous regions of the material. Planar defects
include grain boundaries, stacking faults and external surfaces.

It is important to note at this point that plastic deformation in a material occurs due to the movement of
dislocations (linear defects). Millions of dislocations result for plastic forming operations such as rolling and
extruding. It is also important to note that any defect in the regular lattice structure disrupts the motion of
dislocation, which makes slip or plastic deformation more difficult. These defects not only include the point and
planer defects mentioned above, and also other dislocations. Dislocation movement produces additional
dislocations, and when dislocations run into each other it often impedes movement of the dislocations. This
drives up the force needed to move the dislocation or, in other words, strengthens the material. Each of the
crystal defects will be discussed in more detail in the following pages.

Point Defects

Point defects are where an atom is missing or is in an irregular place in the lattice structure. Point defects
include self interstitial atoms, interstitial impurity atoms, substitutional atoms and vacancies. A self interstitial
atom is an extra atom that has crowded its way into an interstitial void in the crystal structure. Self interstitial
atoms occur only in low concentrations in metals because they distort and highly stress the tightly packed
lattice structure.

A substitutional impurity atom is an atom of a different type than the bulk atoms, which has replaced one of the
bulk atoms in the lattice. Substitutional impurity atoms are usually close in size (within approximately 15%) to
the bulk atom. An example of substitutional impurity atoms is the zinc atoms in brass. In brass, zinc atoms with
a radius of 0.133 nm have replaced some of the copper atoms, which have a radius of 0.128 nm.
Interstitial impurity atoms are much smaller than the atoms in the bulk matrix. Interstitial impurity atoms fit into
the open space between the bulk atoms of the lattice structure. An example of interstitial impurity atoms is the
carbon atoms that are added to iron to make steel. Carbon atoms, with a radius of 0.071 nm, fit nicely in the
open spaces between the larger (0.124 nm) iron atoms.

Appendix D. Page 7 of 116.


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Vacancies are empty spaces where an atom should be, but is missing. They are common, especially at high
temperatures when atoms are frequently and randomly change their positions leaving behind empty lattice
sites. In most cases diffusion (mass transport by atomic motion) can only occur because of vacancies.

Linear Defects - Dislocations

Dislocations are another type of defect in crystals. Dislocations are areas were the atoms are out of position in
the crystal structure. Dislocations are generated and move when a stress is applied. The motion of dislocations
allows slip – plastic deformation to occur.

Before the discovery of the dislocation by Taylor, Orowan and Polyani in 1934, no one could figure out how the
plastic deformation properties of a metal could be greatly changed by solely by forming (without changing the
chemical composition). This became even bigger mystery when in the early 1900’s scientists estimated that
metals undergo plastic deformation at forces much smaller than the theoretical strength of the forces that are
holding the metal atoms together. Many metallurgists remained skeptical of the dislocation theory until the
development of the transmission electron microscope in the late 1950’s. The TEM allowed experimental
evidence to be collected that showed that the strength and ductility of metals are controlled by dislocations.

There are two basic types of dislocations, the edge dislocation and the screw dislocation. Actually, edge and
screw dislocations are just extreme forms of the possible dislocation structures that can occur. Most
dislocations are probably a hybrid of the edge and screw forms but this discussion will be limited to these two
types.

Appendix D. Page 8 of 116.


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Edge Dislocations
The edge defect can be easily visualized as an extra half-plane of atoms in a lattice. The dislocation is called a
line defect because the locus of defective points produced in the lattice by the dislocation lie along a line. This
line runs along the top of the extra half-plane. The inter-atomic bonds are significantly distorted only in the
immediate vicinity of the dislocation line.

Understanding the movement of a dislocation is key to understanding why dislocations allow deformation to
occur at much lower stress than in a perfect crystal. Dislocation motion is analogous to movement of a
caterpillar. The caterpillar would have to exert a large force to move its entire body at once. Instead it moves
the rear portion of its body forward a small amount and creates a hump. The hump then moves forward and
eventual moves all of the body forward by a small amount.

Appendix D. Page 9 of 116.


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As shown in the set of images above, the dislocation moves similarly moves a small amount at a time. The
dislocation in the top half of the crystal is slipping one plane at a time as it moves to the right from its position in
image (a) to its position in image (b) and finally image (c). In the process of slipping one plane at a time the
dislocation propagates across the crystal. The movement of the dislocation across the plane eventually causes
the top half of the crystal to move with respect to the bottom half. However, only a small fraction of the bonds
are broken at any given time. Movement in this manner requires a much smaller force than breaking all the
bonds across the middle plane simultaneously.

Screw Dislocations

There is a second basic type of dislocation, called screw


dislocation. The screw dislocation is slightly more
difficult to visualize. The motion of a screw dislocation is
also a result of shear stress, but the defect line
movement is perpendicular to direction of the stress and
the atom displacement, rather than parallel. To visualize
a screw dislocation, imagine a block of metal with a
shear stress applied across one end so that the metal
begins to rip. This is shown in the upper right image.
The lower right image shows the plane of atoms just
above the rip. The atoms represented by the blue
circles have not yet moved from their original position.
The atoms represented by the red circles have moved
to their new position in the lattice and have
reestablished metallic bonds. The atoms represented
by the green circles are in the process of moving. It can
be seen that only a portion of the bonds are broke at
any given time. As was the case with the edge
dislocation, movement in this manner requires a much
smaller force than breaking all the bonds across the
middle plane simultaneously.

If the shear force is increased, the atoms will continue to


slip to the right. A row of the green atoms will find there way back into a proper spot in the lattice (and become
red) and a row of the blue atoms will slip out of position (and become green). In this way, the screw dislocation
will move upward in the image, which is perpendicular to direction of the stress. Recall that the edge
dislocation moves parallel to the direction of stress. As shown in the image below, the net plastic deformation
of both edge and screw dislocations are the same, however.

The dislocations move along the densest planes of atoms in a material, because the stress needed to move
the dislocation increases with the spacing between the planes. FCC and BCC metals have many dense planes,
so dislocations move relatively easy and these materials have high ductility. Metals are strengthened by
making it more difficult for dislocations to move. This may involve the introduction of obstacles, such as
interstitial atoms or grain boundaries, to “pin” the dislocations. Also, as a material plastically deforms, more

Appendix D. Page 10 of 116.


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dislocations are produced and they will get into each others way and impede movement. This is why strain or
work hardening occurs.

In ionically bonded materials, the ion must move past an area with a repulsive charge in order to get to the next
location of the same charge. Therefore, slip is difficult and the materials are brittle. Likewise, the low density
packing of covalent materials makes them generally more brittle than metals.

Planar Defects

Stacking Faults and Twin Boundaries


A disruption of the long-range stacking sequence can produce two other common types of crystal defects: 1) a
stacking fault and 2) a twin region. A change in the stacking sequence over a few atomic spacing produces a
stacking fault whereas a change over many atomic spacing produces a twin region.

A stacking fault is a one or two layer interruption in the stacking sequence of atom planes. Stacking faults
occur in a number of crystal structures, but it is easiest to see how they occur in close packed structures. For
example, it is know from a previous discussion that face centered cubic (fcc) structures differ from hexagonal
close packed (hcp) structures only in their stacking order. For hcp and fcc structures, the first two layers
arrange themselves identically, and are said to have an AB arrangement. If the third layer is placed so that its
atoms are directly above those of the first (A) layer, the stacking will be ABA. This is the hcp structure, and it
continues ABABABAB. However it is possible for the third layer atoms to arrange themselves so that they are
in line with the first layer to produce an ABC arrangement which is that of the fcc structure. So, if the hcp
structure is going along as ABABAB and suddenly switches to ABABABCABAB, there is a stacking fault
present.

Appendix D. Page 11 of 116.


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Alternately, in the fcc arrangement the pattern is ABCABCABC. A stacking fault in an fcc structure would
appear as one of the C planes missing. In other words the pattern would become ABCABCAB_ABCABC.

If a stacking fault does not corrects itself immediately but continues over some number of atomic spacing, it will
produce a second stacking fault that is the twin of the first one. For example if the stacking pattern is
ABABABAB but switches to ABCABCABC for a period of time before switching back to ABABABAB, a pair of
twin stacking faults is produced. The red region in the stacking sequence that goes
ABCABCACBACBABCABC is the twin plane and the twin boundaries are the A planes on each end of the
highlighted region.

Grain Boundaries in Polycrystals


Another type of planer defect is the grain boundary. Up to this point, the discussion has focused on defects of
single crystals. However, solids generally consist of a number of crystallites or grains. Grains can range in size
from nanometers to millimeters across and their orientations are usually rotated with respect to neighboring
grains. Where one grain stops and another begins is know as a grain boundary. Grain boundaries limit the
lengths and motions of dislocations. Therefore, having smaller grains (more grain boundary surface area)
strengthens a material. The size of the grains can be controlled by the cooling rate when the material cast or
heat treated. Generally, rapid cooling produces smaller grains whereas slow cooling result in larger grains. For
more information, refer to the discussion on solidification.

Bulk Defects

Bulk defects occur on a much bigger scale than the rest of


the crystal defects discussed in this section. However, for
the sake of completeness and since they do affect the
movement of dislocations, a few of the more common bulk
defects will be mentioned. Voids are regions where there
are a large number of atoms missing from the lattice. The
image to the right is a void in a piece of metal The image
was acquired using a Scanning Electron Microscope
(SEM). Voids can occur for a number of reasons. When
voids occur due to air bubbles becoming trapped when a
material solidifies, it is commonly called porosity. When a
void occurs due to the shrinkage of a material as it
solidifies, it is called cavitation.

Another type of bulk defect occurs when impurity atoms cluster together to form small regions of a different
phase. The term ‘phase’ refers to that region of space occupied by a physically homogeneous material. These
regions are often called precipitates. Phases and precipitates will be discussed in more detail latter.

Appendix D. Page 12 of 116.


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Pinning points - overview.

In a crystalline material, a dislocation is capable of traveling throughout the lattice when relatively small
stresses are applied. This movement of dislocations results in the material plastically deforming. Pinning points
in the material act to halt a dislocation's movement, requiring a greater amount of force to be applied to
overcome the barrier. This results in an overall strengthening of materials.

Motion of Dislocations at Elevated Temperatures


Abstract:
The movies, which are in MPG format, show the movement of dislocations in ferritic steels (body-centred cubic crystal
structure), at elevated temperatures. The images are taken in a hot-stage in a transmission electron microscope. These
observations have been used to conclude the molybdenum and tungsten have the same solid-solution strengthening effect
on ferrite

Types of pinning points

Point defects

Point defects (as well as stationary dislocations, jogs, and kinks) present in a material create stress fields
within a material that disallow traveling dislocations to come into direct contact. Much like two particles of the
same electric charge feel a repulsion to one another when brought together, the dislocation is pushed away
from the already present stress field.

Alloying elements

The introduction of atom1 into a crystal of atom2 creates a pinning point for multiple reasons. An alloying atom
is by nature a point defect, thus it must create a stress field when placed into a foreign crystallographic position,
which could block the passage of a dislocation. However, it is possible that the allowing material is
approximately the same size as the atom that is replaced, and thus its presence would not stress the lattice (as
occurs in cobalt alloyed nickel). The different atom would, though, have a different elastic modulus, which
would create a different terrain for the moving dislocation. A higher modulus would look like an energy barrier,
and a lower like an energy trough – both of which would stop its movement.

Appendix D. Page 13 of 116.


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Second phase precipitates

The precipitation of a second phase within the lattice of a material creates physical blockades through which a
dislocation cannot pass. The result is that the dislocation must bend (which requires greater energy, or a greater
stress to be applied) around the precipitates, which inevitably leaves residual dislocation loops encircling the
second phase material and shortens the original dislocation. This is a schematic shows how a dislocation interacts
with solid phase precipitates. The dislocation moves from left to right in each frame.

Dislocation slip mechanism

Grain boundaries

Dislocations require proper lattice ordering to move through a material. At grain boundaries, there is a lattice
mismatch, and every atom that lies on the boundary is uncoordinated. This stops dislocations that encounter
the boundary from moving.

Appendix D. Page 14 of 116.


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Methods of strengthening

Following are brief description s on the methods of strengthening.

Work or Strain hardening

The reason for strain hardening is that the dislocation density increases with plastic deformation (cold work)
due to multiplication. The average distance between dislocations then decreases and dislocations start
blocking the motion of dislocations.

The primary species responsible for work hardening are dislocations. Dislocations interact with each other by
generating stress fields in the material. The interaction between the stress fields of dislocations can impede
dislocation motion by repulsive or attractive interactions. Additionally, if two dislocations cross, dislocation line
entanglement occurs, causing the formation of a jog which opposes dislocation motion. These entanglements
and jogs act as pinning points, which oppose dislocation motion. As both of these processes are more likely to
occur when more dislocations are present, there is a correlation between dislocation density and yield
strength,

Where G is the shear modulus, b is the Burgers vector, and is the dislocation density.

Increasing the dislocation density increases the yield strength which results in a higher shear stress required to
move the dislocations. This process is easily observed while working a material. Theoretically, the strength of a
material with no dislocations will be extremely high (τ=G/2) because plastic deformation would require the
breaking of many bonds simultaneously. However, at moderate dislocation density values of around 107-109
dislocations/m2, the material will exhibit a significantly lower mechanical strength. Analogously, it is easier to
move a rubber rug across a surface by propagating a small ripple through it than by dragging the whole rug. At
dislocation densities of 1014 dislocations/m2 or higher, the strength of the material becomes high once again.
It should be noted that the dislocation density can't be infinitely high because then the material would lose its
crystalline structure.

Work hardening is an important strengthening process in steel, particularly in obtaining high strength levels in
rod and wire, both in plain carbon and alloy steels. For example, the tensile strength of a 0.05% C steel
subjected to 95% reduction in area by wire drawing, is raised by no less than 550 MPa while higher carbon
steels are strengthened by up to twice this amount. Indeed, without the addition of special alloying elements,
plain carbon steels can be raised to strength levels above 1500 MPa simply by the phenomenon of work
hardening.

Basic work on the deformation of iron has largely concentrated on the other end of the strength spectrum,
namely pure single crystals and polycrystals subjected to small controlled deformations. The diversity of slip

Appendix D. Page 15 of 116.


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planes leads to rather irregular wavy slip bands in deformed crystals, as the dislocations can readily move from
one type of plane to another by cross slip, provided they share a common slip direction.

The yield stress of iron single crystals are very sensitive to both temperature and strain rate and a similar
dependence has been found for less pure polycrystalline iron. Therefore, the temperature sensitivity cannot be
attributed to interstitial impurities. It is explained by the effect of temperature on the stress needed to move free
dislocations in the crystal, the Peierls-Nabarro stress.

Case Study 1: The effect of cyclic torsion on the dislocation structure of drawn mild steel

1. Introduction
Cold forming of metals usually causes their work hardening. The magnitude of this hardening depends on the
area reduction, on the temperature and strain rate associated with the processing, and on the way the strain is
imposed on the metal. Keeping all other variables constant, the work hardening of a metal submitted to a
sequential straining under varying directions or of different natures is different from that resulting from
monotonic straining. Changes in the way the material is deformed can alter the hardening rates and even
cause strain softening of the metal1-16.
Recent research results17-19 show that cyclic straining influences in various ways the mechanical behavior of
annealed and drawn metal bars. Annealed Aluminum submitted to cyclic torsion displays higher flow stresses
than the annealed material. On the other hand, cyclic torsion softens previously drawn Aluminum. Cyclic
torsion also softens steel bars previously drawn in one or two passes and hardens the initially annealed
material. Experimental results indicate that the stress-strain curve and the work hardening coefficient (n) of
steel drawn in two passes and submitted to cyclic torsion are similar to those for the material submitted to only
one drawing pass. This is similar to the case of the Aluminum alloy 6063, where the cyclic torsion after two
drawing passes eliminates the hardening associated with the second drawing pass. It is also observed for both
materials that their Ultimate Tensile Strength (UTS) tends to remain unaltered by cyclic torsion, in the case of
initially annealed material, whereas their Yield Strength (YS) is considerably increased by cyclic torsion. The
YS and UTS of both previously drawn materials are decreased by cyclic torsion, with the exception of the YS of
Aluminum drawn in a single pass. The decrease in these properties is more pronounced after two drawing
passes than after a single drawing pass. Finally, cyclic torsion increases the Tensile Elongation to Fracture of
drawn material and decreases this property for initially annealed material.
The present research analyzes the relationship between the mechanical effects described above and the
dislocation structures in Low Carbon steel.

2. Materials and Experimental Methods


The material was an AISI 1010 steel with the following chemical composition: 0.12%C, 0.47%Mn, 0.07%Si,
0.003%Sn, 0.01%Mo, 0.016%P e 0.013%S, received as cylindrical bars 6.4 mm in diameter. The bars were
initially annealed and some of them were drawn in one or two passes. A fraction of these bars were then
submitted to cyclic torsion. The effects of the strain path were analyzed by Transmission Electron Microscopy
(TEM).
Annealing was performed under vacuum, at 850 °C for 2400 seconds, leading to an average hardness of
122.6 HV. Drawing was performed in a hydraulic draw bench, using Tungsten Carbide dies with semi-angle of
8?and abundant lubrication with a Molybdenum Disulfide paste. Different dies were employed, guaranteeing a

Appendix D. Page 16 of 116.


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fixed reduction of area of 20% in each pass. Cyclic torsion (11.2% plastic strain per cycle, total of 10 cycles)
was performed in an especially adapted lathe, where the chuck was manually actuated. All experiments were
performed at room temperature, at a strain rate of 0.002 / s5. All deformed samples were stored at
temperatures below 0 °C in order to avoid static strain aging effects.
TEM was performed in a JEOL-JEM microscope, operated at 200 kV. Analyses were performed in 3 mm
samples taken from the cross-section of the bars. Sample preparation involved initial mechanical polishing,
followed by electrolytic thinning with a perchloric acid and ethanol solution at room temperature.

3. Results and Discussion


The dislocation structures of the annealed and of the drawn material (in one or two passes) are shown in
Figures 1 and The effect of cyclic torsion on the dislocation structure of drawn mild steel2 respectively. The
dislocation density is quite low for the annealed material, whereas the deformed material displays a much
higher dislocation density. Drawn material shows an aligned cell structure, with irregular cell sizes and cell wall
thickness. Dense dislocation networks can be observed inside the cells. Higher drawing strains lead to a
smaller cell size, as expected.

Figure 1. Figure 2a.

.
Figure 2b. TEM of annealed and drawn steel
(8% and 20% per pass) a: 1 pass b: 2 passes

The dislocation structure of the material submitted only to cyclic torsion is broadly similar to that resulting from
drawing (see Figure 3), but the cell size is higher and the tendency to cell alignment is less pronounced than in

Appendix D. Page 17 of 116.


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drawing. It is important to realize that the total strain caused by cyclic torsion is much higher than in drawing,
but leads to essentially similar dislocation structures.

The analysis of Figure 4 indicates that the dislocation structure of the material after one drawing pass is altered
by subsequent cyclic torsion. There is an increase in the cell size, a decrease in their alignment and in the
dislocation density within the cells, and an overall evolution of alignment in only one direction to a
"checkerboard" appearance, which is typical of the development of two sets of aligned cells, corresponding to
the two directions of twisting. This is also the situation for the material initially annealed, drawn in 2 passes and
cyclically twisted (Figure 5). Under these circumstances, the dislocation cells tend to be larger and the
dislocation density inside the cells lower than for one drawing pass followed by cyclic torsion. Cyclic torsion
promotes dynamic recovery of the material, involving the annihilation of cell walls and the decrease of
dislocation density inside the cells. This is similar to results from the analysis of the Bauschinger effect20.
where such dislocation annihilation stems from dislocation movements in opposing directions.

Appendix D. Page 18 of 116.


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Considering the widely established relationship between the material flow stress G, and the corresponding
dislocation density r20:

one should expect higher flow stresses in the drawn or cyclic twisted material than in the annealed material.
On the other hand, the recovery promoted by cyclic torsion of the previously drawn material should lead to their
softening and consequent lower flow stresses.

4. Conclusions
Drawing of low carbon steel leads to the formation of an aligned dislocation structure, displaying irregular cell
sizes and cell wall thickness as well as dense networks of dislocations inside the cells.
Cyclic torsion promotes the softening of material previously strained by drawing. This softening is associated
with a restructuring of the previous dislocation arrangement, involving an increase in cell size, a decrease in
the dislocation density inside the cells and a "checkerboard" dislocation wall structure.

Appendix D. Page 19 of 116.


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Grain Boundary Strengthening

In grain boundary strengthening the grain boundaries act as pinning points impeding further dislocation
propagation. Since the lattice structure of adjacent grains differs in orientation, it requires more energy for a
dislocation to change directions and move into the adjacent grain. The grain boundary is also much more
disordered than inside the grain, which also prevents the dislocations from moving in a continuous slip plane.
Impeding this dislocation movement will hinder the onset of plasticity and hence increase the yield strength of
the material.

Grain boundaries act as an impediment to dislocation motion for the following two reasons:

• Dislocation must change its direction of motion due to the differing orientation of grains.
• Discontinuity of slip planes from grain 1 to grain

Under an applied stress, existing dislocations and dislocations generated by Frank-Read Sources will move
through a crystalline lattice until encountering a grain boundary, where the large atomic mismatch between
different grains creates a repulsive stress field to oppose continued dislocation motion. As more dislocations
propagate to this boundary, dislocation 'pile up' occurs as a cluster of dislocations are unable to move past the
boundary. As dislocations generate repulsive stress fields, each successive dislocation will apply a repulsive
force to the dislocation incident with the grain boundary. These repulsive forces act as a driving force to reduce
the energetic barrier for diffusion across the boundary, such that additional pile up causes dislocation diffusion
across the grain boundary, allowing further deformation in the material.

Decreasing grain boundary size decreases the amount of possible pile up at the boundary, increasing the
amount of applied stress necessary to move a dislocation across a grain boundary. The higher the applied
stress to move the dislocation, the higher the yield strength. Thus, there is then an inverse relationship
between grain boundary size and yield strength, as demonstrated by the Hall-Petch equation. A lower number
of dislocations per grain results in a lower dislocation 'pressure' building up at grain boundaries. This makes it
more difficult for dislocations to move into adjacent grains. This relationship can be mathematically described
as follows:

,
Where k is a constant, d is the average grain diameter and σy,0 is the original yield stress.
However, when there is a large direction change in the orientation of the two adjacent grains, the dislocation
may not necessarily move from one grain to the other but instead create a new source of dislocation in the
adjacent grain. The theory remains the same that more grain boundaries create more opposition to dislocation
movement and in turn strengthens the material.

Appendix D. Page 20 of 116.


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Figure 1: Hall-Petch Strengthening is limited by the size of dislocations. Once the grain size reaches about 10 nm,
grain boundaries start to slide.

Obviously, there is a limit to this mode of strengthening, as infinitely strong materials do not exist. Grain
boundary sizes can range from about 100 μm (large grains) to 1 μm (small grains). Lower than this, the size of
dislocations begins to approach the size of the grains. At a grain size of about 10 nm, only one or two
dislocations can fit inside of a grain (see Figure 1 above). This scheme prohibits dislocation pile-up and never
results in grain boundary diffusion. The lattice resolves the applied stress by grain boundary sliding, resulting in
a decrease in the material's yield strength; A phenomenon known as grain-boundary sliding.

To understand the mechanism of grain boundary strengthening one must understand the nature of
dislocation-dislocation interactions. Dislocations create a stress field around them given by:

Appendix D. Page 21 of 116.


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Where G is the material's shear modulus, and b is the Burgers vector. If the dislocations are in the right
alignment with respect to each other, the local stress fields they create will repel each other. This helps
dislocation movement along grains and across grain boundaries. Hence, the more dislocations are present in a
grain, the greater the stress field felt by a dislocation near a grain boundary:

This is a schematic roughly illustrating the concept of dislocation pile up and how it effects the strength of the
material. A material with larger grain size is able to have more dislocation to pile up leading to a bigger driving
force for dislocations to move from one grain to another. Thus you will have to apply less force to move a
dislocation from a larger than from a smaller grain, leading materials with smaller grains to exhibit higher yield
stress.

In a polycrystalline metal, grain size has a tremendous influence on the mechanical properties. Because grains
usually have varying crystallographic orientations, grain boundaries arise. While an undergoing deformation,
slip motion will take place.

The refinement of the grain size of ferrite provides one of the most important strengthening routes in the heal
treatment of steels. The grain size effect on the yield stress can therefore be explained by assuming that a
dislocation source operates within a crystal causing dislocations to move and eventually to pile up at the grain
boundary. The pile-up causes a stress to be generated in the adjacent grain, which, when it reaches a critical
value, operates a new source in that grain.
In this way, the yielding process is propagated from grain to grain. The grain size determines the distance
dislocations have to move to form grain boundary pile-ups, and thus the number of dislocations involved. With
large grain sizes, the pile-ups will contain larger numbers of dislocations, which will in turn cause higher stress
concentrations in neighboring grains.
In practical terms, the finer the grain size, the higher the resulting yield stress and, as a result, in modern steel
working much attention is paid to the final ferrite grain size. While a coarse grain size of d-1/2 = 2, i.e. d = 0.25

Appendix D. Page 22 of 116.


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mm, gives a yield stress in mild steels of around 100 MPa, grain refinement to d-1/2 = 20. i.e. d = 0.0025 mm,
raises the yield stress to over 500 MPa, so that achieving grain sizes in the range 2-10 μm is extremely
worthwhile.

Appendix D. Page 23 of 116.


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Dispersion Strengthening

(Mechanical Alloying)
Dispersion strengthening is about the interaction between dislocations and finely dispersed particles in the
metal matrix. Traditionally, dispersion particles are obtained as precipitates from phase transformations during
traditional metallurgical processes (melting, solidification, and heat treating). This is the case of many
high-strength commercial alloys. However, maximum service temperatures are limited by the limited thermal
stability of particles or precipitates obtained from thermal processes.

A: Lattice distortion due to the presence of coherent precipitate:


B: Noncohereny precipitates produce no lattice distortion

Particles, which may not be metallurgical compatible with a given metal, can be introduced in a metal matrix by
violently deforming mixtures of different powders. Such technique is called mechanical alloying . An example is
high-energy ball milling. Using this technique, oxides and other highly stable chemical species can be
introduced uniformly into the metal microstructure. A further refinement of this technique allows oxidation and
other chemical reactions to take place during the mixing process, a technique that allegedly promotes the
formation of ultrafine dispersoids as well as allowing control of particle composition and distribution. After
mixing, the powder mixture can then be consolidated and compacted using a number of powder metallurgy
techniques to produce a solid with a very fine grain structure.

Mechanical alloying methods permit the manufacturing of metallic alloys with a number of interesting
properties. Some examples of materials include nanocrystalline and amorphous materials, metastable phases,
and alloys with extended solubility limits. Mechanical alloying was originally developed as a means of raising
the maximum service temperatures of nickel-based superalloys for aircraft gas-turbine applications. As turbine
operating temperatures rose, so too did the demand for materials with increased high-temperature strength
and oxidation resistance. Mechanical alloying avoids many of the problems associated with conventional
melting and solidification processes, and is now used to make a variety of oxide-dispersion-strengthened
(ODS) Fe-Cr, Ni-Cr, and Ni-Cr-gamma superalloys for turbine-engine industrial applications and aluminum
alloys for aircraft structural components. Mechanical alloying may play a key role in the development of future
aerospace systems by enabling the production of even higher performance materials that are difficult or
impossible to make by other methods.

The effectiveness of dispersion strengthening largely depends on (a) mechanical and geometrical
characteristics of the dispersoids, such as hardness, continuity, size, and shape, and (b) their density and
distribution (dispersion factor) in the metal matrix. By controlling process parameters, such as characteristics

Appendix D. Page 24 of 116.


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of the raw powder materials, pressing pressures, atmospheres, cycle time, and temperatures, the
microstructure (e.g., grain size, dispersion size, volume fraction, and distribution) can be tailored for specific
performance requirements. New research initiatives in this field include the synthesis of refractory carbide
nanoparticles and assessment of their use as dispersion strengthening agents, as well as alternative methods
to inoculate the metal matrix.

In all steels there is normally more than one phase present, and indeed it is often the case that several phases
can be recognized in the microstructure. The matrix, which is usually ferrite (bcc structure) or austenite (fcc
structure) strengthened by grain size refinement and by solid solution additions, is further strengthened, often
to a considerable degree, by controlling the dispersions of the other phases in the microstructure. The
commonest other phases are carbides formed as a result of the low solubility of carbon in α-iron. In plain
carbon steels this carbide is normally Fe3C (cementite), which can occur, in a wide range of structures from
coarse lamellar form (pearlite), to fine rod or spheroidal precipitates (tempered steels). In alloy steels, the
same range of structures is encountered, except that in many cases iron carbide is replaced by other carbides,
which are thermodynamically more stable. Other dispersed phases which are encountered include nitrides,
intermetallic compounds, and, in cast irons, graphite.
Most dispersions lead to strengthening, but often they can have adverse effects on ductility and toughness. In
fine dispersions (where ideally small spheres are randomly dispersed in a matrix) are well-defined
relationships between the yield stress, or initial flow stress, and the parameters of the dispersion.
These relationships can be applied to simple dispersions sometimes found in steels, particularly after
tempering, when, in plain carbon steels, the structure consists of spheroidal cementite particles in a ferritic
matrix. However, they can provide approximations in less ideal cases, which are the rule in steels, where the
dispersions vary over the range from fine rods and plates to irregular polyhedral. Perhaps the most familiar
structure in steels is that of the eutectoid pearlite, usually a lamellar mixture of ferrite and cementite. This can
be considered as an extreme form of dispersion of one phase in another, and undoubtedly provides a useful
contribution to strengthening.

Appendix D. Page 25 of 116.


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General behaviour of the powder particles during mechanical alloying processing

Case Study:

Effect of mechanical alloying and Ti addition on solution and ageing treatment of an AA7050 aluminium alloy
http://www.scielo.br/scielo.php?pid=S1516-14392007000200017&script=sci_arttext

Mechanical Alloys & Milling


http://www.scribd.com/doc/3629131/Mechanical-alloying-and-milling-Suryanarayana

Appendix D. Page 26 of 116.


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Solid solution strengthening

This is a schematic illustrating how the lattice is strained by the addition of substitutional and interstitial solute.
Notice the strain in the lattice that the solute atoms cause. The interstitial solute could be carbon in iron for
example. The carbon atoms in the interstitial sites of the lattice create a stress field that impedes dislocation
movement.

http://en.wikipedia.org/wiki/Strengthening_mechanisms_of_materials

A grain boundary in a 2D lattice is the interface between two regions of crystalline order. Each region or 'grain'
has a different orientation with respect to some arbitrary axis perpendicular to the plane of the lattice.

Grain boundaries

A vacancy is a point defect that arises when an atom is 'missing' from the ideal crystal structure.

A vacancy
A solute atom in a crystal structure is an atomic species that is different from the majority of atoms that form the

Appendix D. Page 27 of 116.


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structure. Solute atoms of similar size to those in the host lattice may substitute for host atoms - these are
known as substitutional solutes. Solute atoms that are much smaller than the host atoms may exist within
normally empty regions (interstices) in the host lattice, where they are called interstitial solutes.

Substitutional and interstitial solutes.


Note that some distortion of the host lattice occurs around the solutes. A dislocation in a 2D close-packed
plane can be described as an extra 'half-row' of atoms in the structure. Dislocations can be characterised by
the Burgers vector which gives information about the orientation and magnitude of the dislocation.

Dislocation

http://www.msm.cam.ac.uk/doitpoms/tlplib/dislocations/dislocations_in_2D.php

Appendix D. Page 28 of 116.


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Solid solution strengthening by interstitials


The formation of interstitial atmospheres at dislocations requires diffusion of the solute. As both carbon and
nitrogen diffuse much more rapidly in iron than substitutional solutes, it is not surprising that strain ageing can
take place readily in the range from 20°C to 150°C. Consequently the atmosphere condenses to form rows of
interstitial atoms along the cores of the dislocations. These arise because the temperature is high enough to
allow interstitial atoms to diffuse during deformation, and to form atmospheres around dislocations generated
throughout the stress-strain curve. Steels tested under these conditions also show low ductility, due partly to
the high dislocation density and partly to the nucleation of carbide particles on the dislocations where the
carbon concentration is high. The phenomenon is often referred to as blue brittleness, blue being the
interference color of the steel surface when oxidized in this temperature range.
The break away of dislocations from their carbon atmospheres as a cause of the sharp yield point became a
controversial aspect of the theory because it was found that the provision of free dislocations, for example, by
scratching the surface of a specimen, did not eliminate the sharp yield point. An alternative theory was
developed which assumed that, once condensed carbon atmospheres are formed in iron, the dislocations
remain locked, and the yield phenomena arise from the generation and movement of newly formed
dislocations.
To summarize, the occurrence of a sharp yield point depends on the occurrence of a sudden increase in the
number of mobile dislocations. However, the precise mechanism by which this takes place will depend on the
effectiveness of the locking of the pre-existing dislocations. If the pinning is weak, then the yield point can arise
as a result of unpinning. However, if the dislocations are strongly locked, either by interstitial atmospheres or
precipitates, the yield point will result from the rapid generation of new dislocations.
Under conditions of dynamic strain ageing, where atmospheres of carbon atoms form continuously on
newly-generated dislocations, it would be expected that a higher density of dislocations would be needed to
complete the deformation, if it is assumed that most dislocations which attract carbon atmospheres are
permanently locked in position.

Strengthening at high interstitial concentrations


Austenite can take into solid solution up to 10% carbon, which can be retained in solid solution by rapid
quenching. However, in these circumstances the phase transformation takes place, not to ferrite but to a
tetragonal structure referred to as martensite. This phase forms as a result of diffusion less shear
transformation leading to characteristic laths or plates.
If the quench is sufficiently rapid, the martensite is essentially a supersaturated solid solution of carbon in a
tetragonal iron matrix, and as the carbon concentration can be greatly in excess of the equilibrium
concentration in ferrite, the strength is raised very substantially. High carbon martensites are normally very
hard but brittle, the yield strength reaching as much as 1500 MPa; much of this increase can be directly
attributed to increased interstitial solid solution hardening, but there is also a contribution from the high
dislocation density, which is characteristic of martensitic transformations in iron-carbon alloys.

Substitutional solid solution strengthening of iron


Many metallic elements form solid solutions in γ- and α-iron. These are invariably substitutional solid solutions,
but for a constant atomic concentration of alloying elements there are large variations in strength. Using single
crystal data for several metals, Fig. 1 shows that an element such as vanadium has a weak strengthening
effect on α-iron at low concentrations (< 2%), while silicon and molybdenum are much more effective

Appendix D. Page 29 of 116.


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strengthened. Other data indicates that phosphorus; manganese, nickel and copper are also effective
strengtheners. However, it should be noted that the relative strengthening might alter with the temperature of
testing, and with the concentrations of interstitial solutes present in the steels.

Figure 1. Solid solution strengthening of iron crystals by substitutional solutes. Ratio of the critical resolved shear stress τ0
to shear modulus μ as a function of atomic concentration.

The strengthening achieved by substitutional solute atoms is, in general, greater the larger the difference in
atomic size of the solute from that of iron, applying the Hume-Rothery size effect. However, from the work of
Fleischer and Takeuchi it is apparent that differences in the elastic behavior of solute and solvent atoms are
also important in determining the overall strengthening achieved.
In practical terms, the contribution to strength from solid solution effects is superimposed on hardening from
other sources, e.g. grain size and dispersions. Also it is a strengthening increment, like that due to grain size,
which need not adversely affect ductility. In industrial steels, solid solution strengthening is a far from negligible
factor in the overall strength, where it is achieved by a number of familiar alloying elements, e.g. manganese,
silicon, nickel, molybdenum, several of which are frequently present in a particular steel and are additive in
their effect. These alloying elements arc usually added for other reasons, e.g. Si to achieve deoxidation, Mn to
combine with sulphur or Mo to promote hardenability. Therefore, the solid solution hardening contribution can
be viewed as a useful bonus.

Appendix D. Page 30 of 116.


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Precipitation Hardening

In most binary systems, alloying above a concentration given by the phase diagram will cause the formation of
a second phase. A second phase can also be created by mechanical or thermal treatments. The particles that
compose the second phase precipitates act as pinning points in a similar manner to solutes, though the
particles are not necessarily single atoms.
The dislocations in a material can interact with the precipitate atoms in one of two ways (see Figure 2). If the
precipitate atoms are small, the dislocations would cut through them. As a result, new surfaces (b in Figure 2)
of the particle would get exposed to the matrix and the particle/matrix interfacial energy would increase. For
larger precipitate particles, looping or bowing of the dislocations would occur which results in dislocations
getting longer. Hence, at a critical radius of about 5nm, dislocations will preferably cut across the obstacle
while for a radius of 30nm, the dislocations will readily bow or loop to overcome the obstacle.

Appendix D. Page 31 of 116.


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Chapter Two:

The Effects of Alloying Elements on Iron-Carbon Alloys

Effects of Alloying Additions to Steel

Element Influence Uses

Hardness - Strength - Wear


Most important alloying element. Is essential to the
formation of cementite and other carbides, bainite and Added to construction steels to increase
Carbon
iron-carbon martensite. Within limits increasing the strength, hardness and hardenability.
carbon content increases the strength and hardness of a
steel while reducing its toughness and ductility.

Aluminum Deoxidation - Ease of Nitriding

Boron Hardenability

Copper Corrosion Resistance - Strength

Lead Machinability

Phosphorus Strength

Silicon Deoxidation - Hardenability

Sulfur Machinability

Tellurium Machinabilty

Toughness - Strength - Hardenability


Used up to help refine grain size. Used in
Stabilises gamma phase by raising A4 and lowering A3.
large amounts in stainless and
Refines grains in steels and some non-ferrous alloys.
heat-resisting steels.
Strengthens ferrite by solid solution. Unfortunatly is a
Nickel Nickel based alloys can offer corrosion
powerful graphitiser.
resistance in more aggressive environments
Can take into solid solution larger proportions of
and nickel is used as the basis of complex
important elements such as chromium, molybdenum
superalloys for high temperature service.
and tungsten than can iron.

Strength - Hardenability - More Response To Heat


Treatment High manganese (Hadfield) steel contains
Manganese Deoxidises the melt. Greatly increases the hadenability 12.5% Mn and is austenitic but hardens on
of steels. Stabilises gamma phase. Forms stable abrasion.
carbides.

De-oxidises melt. Helps casting fluidity. Improves Up to 0.3% in steels for sandcasting, up to
Silicon
oxidation resistance at higher temperatures. 1% in heat resisting steels.

Appendix D. Page 32 of 116.


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Corrosion Resistance - Strength


Small amounts in constructional and tool
Stabilises alpha phase by raising A3 and depressing A4.
steels. About 1.5% in ball and roller
Chromium Forms hard stable carbides. Strengthens ferrite by solid
bearings. Larger amounts in Stainless and
solution. In amounts above 13% it imparts stainless
heat-resisting steels.
properties. Unfortunately increases grain growth.

High Temperature Strength - Hardenability


Strong carbide-stabilising influence. Raises high
temperature creep strength of some alloys. Slows
tempering response.
Reduces 'temper brittleness' in
When added to stainless steels it greatly improves the
nickel-chromium steels. Increases
Molybdenum pitting and crevice corrosion resistance. There are
red-hardness of tool steels. Now used to
limits to the proportion that can be taken into an iron
replace some tungsten in high-speed steels.
based matrix. However up to almost 30% can be
incorporated into nickel based alloys which provides
excellent corrosion resistance in many aqueous
environments.

Fine Grain - Toughness


Strong carbide forming tendency. Stabilises martensite Used to retain high temperature hardness,
Vanadium and increases hardenability. Restrains grain growth. e.g. in dies for hot-forging and die casting
Improves resistance to softening at elevated dies. Increasingly used in high speed steels.
temperatures after hardening.

Used in high-speed steels and other tool


and die steels, particularly those for use at
high temperatures.
Stabilises alpha phase and forms stable, very hard
Used in a few stainless steels, in
carbides, which improves creep resistance and renders
Tungsten combination with molybdenum. to improve
transformations very sluggish, hence hardened steels
pitting and crevice corrosion resistance. It
resist tempering influences.
is also used in some high temperature
nickel based alloys and in some high
temperature austenitic stainless steels.

Hardness - Wear
Has similar corrosion resistance to that of Nickel, but
higher cost means that it is not normally used for such
applications. Used in super high speed steels and
Cobalt Provides matrix - strengthening characteristics to maraging steels, permanent magnet steels
stainless and nickel based alloys designed for high and alloys.
temperature applications.
Slows the transformation of martensite, hence
increases 'red hardness' which is useful in tool steels.

Elimination Of Carbide Precipitation


Niobium Used to stabilize stainless steels.
In low alloy steels it acts as a carbide former and

Appendix D. Page 33 of 116.


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improves creep resistance.


In stainless steels it combines with carbon, stabilising
the steel and reducing the susceptibility to intergranular
corrosion

Elimination Of Carbide Precipitation Used in stabilized stainless steels.


Titanium In stainless steels combines with excess carbon In nickel based alloys it is used with
reducing the risk of intergranular corrosion. aluminium to promote age hardening.

Appendix D. Page 34 of 116.


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Introduction

Typical 'mild' steels have a small carbon content, usually under 0.2%. Increasing the carbon content hardens
the steel and its ability to take and hold an edge but at the expense of toughness. Adding other alloying
elements can alter these properties, though usually at the expense of increased cost and manufacturability.
The main alloying elements, and their effects are describe in next section. Carbon steels usually contain less
than 1 to 2% carbon and small quantities of manganese, copper, silicon, sulfur, and phosphorus. Alloy steels
are carbon steel with other metals added specifically to improve the properties of the steel
significantly. Stainless steel is considered a separate group. Plain carbon steel is produced with a wide range
of mechanical properties with comparatively low cost. To extend the range of properties of steel, alloys have
been developed. The benefits resulting include

• The maximum UTS is increased.


• Thick sections steels are available with high hardness throughout the section.
• More controllable quenching with minimum risk of shape distortion or cracking.
• Improved impact resistance at high temperature range.
• Improved corrosion resistance.
• Improved high temperature performance.

The principle elements that are used in producing alloy steel include nickel, chromium, molydenenum,
manganese, silicon and vanadium. Cobalt, copper and lead are also used as alloying elements.

Effect of alloying elements

Elements may encourage formation of graphite from the carbide. Only a small proportion of
these elements can be added to the steel before graphite forms destroying the properties of the
steel, unless elements are added to counteract the effect.

Elements which encourage the formation of graphite include silicon, cobalt, aluminium and nickel

Alloying elements may go into solid solution in the iron, enhancing the strength. Elements which
go into solid solution include silicon, molybdenum, chromium, nickel and magnesium.

Hard carbides (cementite) associated with iron and carbon may be formed with alloying
elements. Elements which tend to form carbides include chromium, tungsten, titanium,
columbium, vanadium, molybdenum and manganese.

Elements which stabilize austenite include manganese, nickel, cobalt and copper. These
increase the range over which austenite is stable e.g. by lowering the eutectoid temperature, and
this retards the separation or carbides. If these alloys are present is certain high levels the
austenite phase is dramatically reduced and the ferrite ( α) phase exists down to ambient
temperatures e.g.18% chromium .

Appendix D. Page 35 of 116.


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Elements which tend to stabilize ferrite include chromium, tungsten, molybdenum, vanadium and
silicon. They reduce the amount of carbon soluble in the austenite and thus increase the volume
of free carbide in the steel at a given carbon content. The effectively reduce the austenite ( γ )
phase by raising the eutectoid temperature and lowering the peritectic temperature

Intermediate compounds with iron may be formed e.g. FeCr

Alloying elements may adjust the characteristics such as eutectoid content, quenching rate
which produces bainite or martensite.

Relative effect alloying elements

The combined effect of alloying elements results from many complex interactions resulting from
the processing history, the number and quantities of constituents, the heat treament, the section
shape etc. Some basic rules can be identified.

Nickel has reduced carbide forming tendency than iron and dissolves in α ferrite.
Silicon combines with oxygen to form nonmetallic inclusions or dissolves in the ferrite.
Most of the manganese in alloy steels dissolves in the α ferrite . Any manganese that form
carbides result in (Fe,Mn)3C.
Chromium spreads between the ferrite and carbide phases the spread depending on the amount
of carbon and other carbide generating elements present.
Tungsten and molybdenum form carbides if sufficient carbon is present which has not already
formed carbides with other stronger carbide forming elements.
Vanadium , titanium, and Colombian are strong carbide forming elements and are present in
steel as carbides.
Aluminium combines with oxygen and nitrogen to form Al2O an AlN

Appendix D. Page 36 of 116.


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Characteristics of alloying

Effects of Elements on Steel


Steels are among the most commonly used alloys. The complexity of steel alloys is fairly significant. Not all
effects of the varying elements are included. The following text gives an overview of some of the effects of
various alloying elements. Additional research should be performed prior to making any design or engineering
conclusions.

The Periodic Table:

The Atomic Radii:

Appendix D. Page 37 of 116.


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In specifying values for the radius of an atom, one must keep in mind the fact that atoms are not
hard spheres, and the electron distribution in the outer part of the atom does not have a sharp
cutoff radius. You could characterize the radius of the atom as a limiting radius where a certain
percentage of the electron charge will be found. The illustration above is a plot of "covalent radii"
(from Ebbing) which are determined by measuring the bond lengths in the molecules of chemical
compounds. Another way to determine characteristic radii is to measure ionic radii in crystals
using x-ray diffraction. If the crystalline composition is such that the ions can be considered to be
in contact with each other, and you can determine the lattice spacing from x-ray diffraction, then
you can imply the ionic radius. As might be expected, the ionic radius of negative ions is slightly
larger than the covalent radius since they have extra electronic charge, and that of positive ions is
slightly smaller.

Atoms and Nuclei


http://www.practicalphysics.org/go/Topic_40.html?topic_id=40

Appendix D. Page 38 of 116.


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Carbon

Carbon has a major effect on steel properties. Carbon is the primary hardening element in steel. Hardness
and tensile strength increases as carbon content increases up to about 0.85% C as shown in the figure
above. Ductility and weldability decrease with increasing carbon.

Carbon is essential in steels which have to be hardened by quenching and for example, in austenitic
manganese steel which is required to have high resistance to wear. The maximum hardness obtainable in any
carbon steel is a function of the carbon content which may vary up to about 2% according to the purpose for
which the steel is to be used. It occurs in varying forms according to the percentage present, and the heat
treatment to which the steel has been submitted. (See allotropy and transformation range). Cast irons usually
contain from about 1.8% to 4.5% carbon, present either as free carbon (graphite) and/or combined carbon
(cementite), the varying distribution of the carbon between these two forms considerably influencing the
strength and hardness.

Carbon is a strong austenite former and strongly promotes an austenitic structure. It also substantially
increases the mechanical strength. Carbon reduces the resistance to intergranular corrosion. In ferritic
stainless steels carbon will strongly reduce both toughness and corrosion resistance. In the martensitic and
martensitic-austenitic steels carbon increases hardness and strength. In the martensitic steels an increase in
hardness and strength is generally accompanied by a decrease in toughness and in this way carbon reduces
the toughness of these steels.

Carbon: Present in all steels, it is the most important hardening element. Also increases the strength of the
steel. We usually want knife-grade steel to have >.5% carbon, which makes it "high-carbon" steel.

it has by far the greatest influence of any of the elements. Steel could not exist without carbon. Martensite,
along with banite gives steel a microstructure of hard, tough carbide. None of the other elements so
dramatically alter the strength and hardness as do small changes in carbon content. Carbon
iron crystalline structures have the widest number and variety known to exist in metallurgy. They also
combine with other elements to furnish steel with an assortment of iron alloy carbide systems.

Appendix D. Page 39 of 116.


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Manganese

Manganese fulfils a variety of functions in steel.

ƒ It is used as a deoxidizing agent in nearly all steels.


ƒ It forms manganese sulphide inclusions which in the ingot are spherical. In the absence of
manganese sulphur forms interdendritic films of iron sulphide causing brittleness at forging
temperature (hot shortness).
ƒ It effectively increases harden ability and up to 1.5% is added for this purpose. (d) In larger amounts
it is used to stabilize austenite, as in 14% manganese steel.

MANGANESE (Mn): Is normally present in all steel and functions as a deoxidizer. It also imparts strength
and responsiveness to heat treatment. It is usually present in quantities of 0.5 to 2.0 percent. Range 0.3% to
1.5% always present in steels to reduce the negative effects of impurities carried out forward from the
production process e.g. sulphur embrittlement. It promotes the formation of stable carbides in
quenched-hardened steels. Alloys containing manganese are pearlitic. Up to 1% acts as hardening agent and
from 1% to 2% improves strength and toughness. Alloys containing more than 5% are non-magnetic. Alloys
containing large proportions of up to 12.5% manganese have the property that they spontaneously form hard
skins when subject to abrasion. (Self-hardening)

All commercial steels contain 0.3-0.8% manganese, to reduce oxides and to counteract the harmful influence
of iron sulfide. Any manganese in excess of these requirements partially dissolves in the iron and partly forms
Mn3C which occurs with the Fe3C. There is a tendency nowadays to increase the manganese content and
reduce the carbon content in order to get steel with an equal tensile strength but improved ductility
If the manganese is increased above 1,8% the steel tends to become air hardened, with resultant impairing of
the ductility. Up to this quantity, manganese has a beneficial effect on the mechanical properties of oil
hardened and tempered 0.4% carbon steel. The manganese content is also increased in certain alloy steels,
with a reduction or elimination of expensive nickel, in order to reduce costs. Steels with 0.3-0.4% carbon,
1,3-1,6% manganese and 0.3% molybdenum have replaced 3% nickel steel for some purposes.

Non-shrinking tool steel contains up to 2% manganese, with 0.8-0.9% carbon. Steels with 5 to 12%
manganese are martensitic after slow cooling and have little commercial importance.

Hadfield`s manganese steel a specially steel which is austenitic and usually contains approximately
12% Manganese. It is used in mining, earth- moving equipment and in railroad track work. .
Hadfield`s manganese steel contains 12 to 14% of manganese and 1,0% of carbon. It is characterized by a
great resistance to wear and is therefore used for railway points, rock drills and stone crushers. Austenite is
completely retained by quenching the steel from 1000°C, in which soft condition it is used, but abrasion raises
the hardness of the surface layer from 200 to 600 VPN (with no magnetic change), while the underlying
material remains rough. Annealing embrittles the steel by the formation of carbides at the grain boundaries.
Nickel is added to electrodes for welding manganese steel and 2% Mo sometimes added, with a prior carbide
dispersion treatment at 600°C, to minimize initial distortion and spreading.

Appendix D. Page 40 of 116.


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http://www.arema.org/eseries/scriptcontent/custom/e_arema/library/2
005_Conference_Proceedings/00040.pdf

Manganese is generally beneficial to surface quality especially in resulfurized steels. Manganese contributes
to strength and hardness, but less than carbon. The increase in strength is dependent upon the carbon
content. Increasing the manganese content decreases ductility and weldability, but less than carbon.
Manganese has a significant effect on the hardenability of steel.

Manganese aids the grain structure, and contributes to hardenability, strength & wear resistance. Improves the
steel (e.g. deoxidizes) during the steel's manufacturing (hot working and rolling). Present in most cutlery steel
except for A-2, L-6 and CPM 420V. Manganese slightly increases the strength of ferrite, and also increases the
hardness penetration of steel in the quench by decreasing the critical quenching speed. This also makes the
steel more stable in the quench. Steels with manganese can be quenched in oil rather than water, and
therefore are less susceptible to cracking because of a reduction in the shock of quenching. Manganese is
present in most commercially made steels.

Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the
ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at
high temperatures it will stabilize ferrite. Manganese increases the solubility of nitrogen and is used to obtain
high nitrogen contents in austenitic steels.

Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray

Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the
ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at
high temperatures it will stabilise ferrite. Manganese increases the solubility of nitrogen and is used to obtain
high nitrogen contents in austenitic steels.

Appendix D. Page 41 of 116.


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Figure 2: Typical duplex oxide–sulfide inclusion (particle A, B and C) and plate-like MnS (particle D) in conventional
continuous casting silicon steel.

SEM of an inclusion.

Appendix D. Page 42 of 116.


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Nickel

ƒ Increase Strength.
ƒ Improve Toughness.
ƒ Unable to increase Hardness
ƒ Ferrite Former.

NICKEL (Ni): Increases strength and toughness but is ineffective in increasing hardness. It is generally
added in amounts ranging from 1 percent to 4 percent. In some stainless steels it is sometimes as high as 20
percent. It is used for strength, corrosion resistance, and toughness, nickel increases the strength of ferrite,
therefore increasing the strength of the steel. It is used in low alloy steels to increase toughness and
hardenability. Nickel also tends to help reduce distortion and cracking during the quenching phase of heat
treatment.

Nickel is a ferrite strengthener. Nickel does not form carbides in steel. It remains in solution in
ferrite, strengthening and toughening the ferrite phase. Nickel increases the hardenability and impact strength
of steels. Range 0.2% to 5% Improves strength, toughness, and hardenability without seriously affecting the
ductility. It encourages grain refinement. Nickel and chromium together have opposing properties and are
used together to advantage in nickel-chrome steels. The resulting steels have their advantages combined
and their undesirable features cancel each other At 5% nickel provides high fatigue resistance. When alloyed
at higher proportions significant corrosion resistance results and at 27% a non magnetic stainless steel results.

The addition of nickel, in amounts up to 8% or 10 %, to low carbon steel, increases the tensile strength and
considerably raises the impact resistance. 9% nickel steels are useful at very low temperatures. In
engineering steels it is widely used, often with chromium and molybdenum. High nickel increases resistance
to corrosion, and in combination with chromium, is used in the austenitic corrosion-resisting steels. Certain
iron-nickel alloys have unique properties. 25% nickel steel is practically non-magnetic. Alloys with about 36%
nickel have very low coefficients of expansion, whilst with 50% to 78.5% nickel; alloys are obtained having
very high magnetic permeability in low fields. An alloy containing 29% nickel, 17% cobalt is used for sealing
with certain borosilicate glasses.

For stainless steel, the main reason for the nickel addition is to promote an austenitic structure. Nickel
generally increases ductility and toughness. It also reduces the corrosion rate and is thus advantageous in acid
environments. In precipitation hardening steels nickel is also used to form the intermetallic compounds that are
used to increase the strength.

Nickel and manganese are very similar in behavior and both lower the eutectoid temperature. This change
point on heating is lowered progressively with increase of nickel (approximately 10°C for 1% of nickel), but the
lowering of the change on cooling is greater and irregular. The temperature of this change (Ar1) is plotted for
different nickel contents for 0.2% carbon steels in Fig. 1, It will be seen that the curve takes a sudden plunge
round about 8% nickel. A steel with 12% nickel begins to transform below 300°C on cooling, but on reheating
the reverse change does not occur until about 650°C. Such steels are said to exhibit pronounced lag or
hysteresis and are called irreversible steels. This characteristic is made use of in maraging steels and 9% Ni

Appendix D. Page 43 of 116.


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cryogenic steel.

It Increases strength and toughness but is ineffective in increasing hardness. It is generally added in amounts
ranging from 1 percent to 4 percent. In some stainless steels it is sometimes as high as 20 percent.

Maraging steels are a class of high-strength steel with low carbon content and the use of
substitutional (as opposed to interstitial) elements to produce hardening from formation of nickel
martensites. The name maraging has resulted from the combination of

Martensite + Age hardening

Maraging steels contain 18% nickel, along with a amounts of molybdenum, cobalt, and titanium
and aluminium, and almost no carbon. These alloys can be strengthened significantly by a
precipitation reaction at a relatively low temperature. They can be formed and machined in the
solution-annealed condition but not without difficulty. Weldability is excellent. Fracture
toughness of the maraging steels is considerably higher than that of the conventional
high-strength steels. Maraging steels are hardened by a metallurgical reaction that does not
involve carbon. Maraging steels are strengthened by intermetallic compounds such as Ni 3Ti
and Ni 3Mo which precipitate at about 500°C. The carbon content provides no real benefit and is
kept low as possible in order to minimize the formation of titanium carbide which can adversely
affect mechanical properties. Toughness is superior to all low alloy carbon steels of similar
strength, particularly the low temperature toughness. These steels are easy to machine and
heat treat, so some cost savings result in component production to compensate for the high cost
of the steel. A high strength maraging steel (extrusion section MIL-S-46850 grade 300) can have
a 0.2% proof stress of 1930MPa and Ultimate Tensile strength of 2068 MPa with an elongation
of 4%

The addition of nickel acts similarly to increasing the rate of cooling of a carbon steel. Thus with a constant rate
of cooling the 5 to 8% nickel steels become troostitic; at 8 to 10% nickel, where the sudden drop appears, the
structure is martensitic, while above 24% nickel the critical point is depressed below room temperature and
austenite remains. The lines of demarcation are not so sharp as indicated by Fig. 1, but a gradual transition
occurs from one constituent to another.

Appendix D. Page 44 of 116.


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Figure1. Effect of nickel on change points and mechanical properties of 0.2% carbon steels cooled at a constant rate.

The mechanical properties change accordingly as shown in the lower part of Fig. 1. Steels with 0.5% nickel are
similar to carbon steel, but are stronger, on account of the finer pearlite formed and the presence of nickel in
solution in the ferrite. When 10% nickel is exceeded the steels have a high tensile strength, great hardness,
but are brittle, as shown by the Izod and elongation curves. When the nickel is sufficient to produce austenite
the steels become non-magnetic, ductile, tough and workable, with a drop in strength and elastic limit.

Carbon intensives the action of nickel and the change points shown in Fig. 1 will vary according to the carbon
content. The influences of carbon and nickel on the structure are shown in the small inset (Guillet) diagram in
Fig. 1, for one rate of cooling. Steels containing 2 to 5% nickel and about 0.1% carbon are used for case
hardening; those containing 0.25 to 0.40% carbons are used for crankshafts, axles and connecting rods.

The superior properties of low nickel steels are best brought out by quenching and tempering (550-650°C).
Since the Ac3 point is lowered, a lower hardening temperature than for carbon steels is permissible and also a
wider range of hardening temperatures above Ac3 without excessive grain growth, which is hindered by the
slow rate of diffusion of the nickel. Martensitic nickel steels are not utilized and the austenitic alloys cannot
compete with similar manganese steels owing to the higher cost. Maraging steels have fulfilled a high tensile
requirement in aero and space fields. High nickel alloys are used for special purposes, owing to the marked

Appendix D. Page 45 of 116.


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influence of nickel on the coefficient of expansion of the metal. With 36% nickel, 0.2% carbon, 0.5%
manganese, the coefficient is practically zero between 0°C and 100°C. This alloy ages with time, but this can
be minimized by heating at 100°C for several days.

The alloy is called Inver and it is used extensively in clocks, tapes and wire measures, differential expansion
regulators, and in aluminum pistons with a split skirt in order to give an expansion approximating to that of cast
iron. A carbon-free alloy containing 78.5% nickel and 21.5% iron has a high permeability in small magnetic
fields.

Figure 6: Vertical section of Fe-Cr-C diagram for 0.1C wt%.

Figure 7: Schaeffler diagram for weld metals.

Appendix D. Page 46 of 116.


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Chromium

Chromium is commonly added to steel to increase corrosion resistance and oxidation resistance, to increase
hardenability, or to improve high-temperature strength. As a hardening element, Chromium is frequently used
with a toughening element such as nickel to produce superior mechanical properties. At higher temperatures,
chromium contributes increased strength. Chromium is strong carbide former. Complex chromium-iron
carbides go into solution in austenite slowly; therefore, sufficient heating time must be allowed for prior to
quenching.

It is added for wear resistance, hardenability, and (most importantly) for corrosion resistance. As with
manganese, chromium has a tendency to increase hardness penetration. When 5 percent chromium or more
is used in conjunction with manganese, the critical quenching speed is reduced to the point that the steel
becomes air hardening. Chromium can also increase the toughness of steel, as well as the wear resistance.

As an alloying element in steel, chromium increases the hardenability and in association with high carbon
gives resistance to abrasion and wear. 4%is present in high speed steel and up to 5% is present in hot die
steels. In Structural steels it may be present in amounts up to about 3 %. Simple chromium-carbon steels are
used for ball bearings having high elastic limit and high uniform hardness due to the uniform distribution of the
hard carbide particles, but for most structural purposes chromium is used in conjunction with up to 4 % nickel
and small amounts of molybdenum or vanadium. In heat-resisting steels, chromium is present in amounts up
to 30%, and it is an important element in many of the highly alloyed heat-resisting materials, whose iron
contents are so low that they cannot be regarded as steel. Chromium is also used as an alloying addition to
high duty cast irons.

This is the most important alloying element in stainless steels. It is this element that gives the stainless steels
their basic corrosion resistance. The corrosion resistance increases with increasing chromium content. It also
increases the resistance to oxidation at high temperatures. Chromium promotes a ferritic structure. Chromium
is unique in its effect on resistance to corrosion and scaling and is an essential constituent in all stainless
steels, e.g., stainless cutlery steels contain 12% to 14% chromium, whilst in steels of the austenitic
corrosion-resisting type, 18% chromium is associated with 8% nickel, and small amounts of other elements.
Steel with at least 13% chromium is deemed "stainless" steel. Despite the name, all steel can rust if not
maintained properly. Chromium can dissolve in either alpha- or gama-iron, but, in the presence of carbon, the
carbides formed are cementite (FeCr)3C in which chromium may rise to more than 15%; chromium carbides
(CrFe)3C2 (CrFe)7C3 (CrFe)4C, in which chromium may be replaced by a few per cent, by a maximum of 55%
and by 25% respectively. Stainless steels contain Cr4C. The pearlitic chromium steels with, say, 2% chromium
are extremely sensitive to rate of cooling and temperature of heating before quenching;

It increases the depth penetration of hardening and also the responsiveness to heat treatment. It is usually
added with nickel (Ni) for use in stainless steels. Most of the chromium (Cr) bearing alloys contain 0.50 to
1.50 percent chromium; some stainless steels contain as much as 20 percent or more. It can affect forging,
causing a tendency in the steel to crack.

Appendix D. Page 47 of 116.


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For example:

Critical Hardening Rate


Temperature of Initial Heating, °C
(Min. to cool from 836°C to 546°C)
836 3.5 S
1010 6.5 S
1200 13 S

The reason is that the chromium carbides are not readily dissolved in the austenite, but the amount increases
with increase of temperature. The effect of the dissolved chromium is to raise the critical points on heating (Ac)
and also on cooling (Ar) when the rate is slow. Faster rates of cooling quickly depress the Ar points with
consequent hardening of the steel. Chromium imparts a characteristic form of the upper portion of the
isothermal transformation curve.
The percentage of carbon in the pearlite is lowered. Hence the proportion of free cementite (hardest
constituent) is increased in high carbon steel and, when the steel is properly heat-treated, it occurs in the
spheroidised form which is more suitable when the steel is used for ball bearings. The pearlite is rendered fine.
When the chromium exceeds 1.1% in low-carbon steels an inert passive film is formed on the surface which
resists attack by oxidizing reagents. Still higher chromium contents are found in heat-resisting steel.

Chromium steels are easier to machine than nickel steels of similar tensile strength. The steels of higher
chromium contents are susceptible to temper brittleness if slowly cooled from the tempering temperature
through the range 550/450°C. These steels are also liable to form surface markings, generally referred to as
"chrome lines". The chrome steels are used wherever extreme hardness is required, such as in dies, ball
bearings, plates for safes, rolls, files and tools. High chromium content is also found in certain permanent
magnets.

Figure 2. Effect of alloying with chromium on the critical temperature of steel and austenite (g -iron) phase transformation
zone on the iron-iron carbide diagram.

Appendix D. Page 48 of 116.


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Nickel and chromium

Nickel steels are noted for their strength, ductility and toughness, while chromium steels are characterized by
their hardness and resistance to wear. The combination of nickel and chromium produces steels having all
these properties, some intensified, without the disadvantages associated with the simple alloys. The depth of
hardening is increased, and with 4,5% nickel, 1,25% chromium and 0.35% carbon the steel can be hardened
simply by cooling in air.
Low nickel-chromium steels with small carbon content are used for casehardening, while for most
constructional purposes the carbon content is 0.25-0.35%, and the steels are heat-treated to give the desired
properties. Considerable amounts of nickel and chromium are used in steel for resisting corrosion and
oxidation at elevated temperatures.
Embattlement. The effects of tempering a nickel-chromium steel are shown in Fig. 2, from which it will be
noticed that the Izod impact curve No. 1 reaches a dangerous minimum in the range 250-450°C in common
with many other steels. This is known as 350°C embattlement. Phosphorus and nitrogen have a significant
effect while other impurities (As, Sb, Sn) and manganese in larger quantity may also contribute to the
embattlement.

Figure 2. Effect of tempering on the mechanical properties of nickel-chromium steel, C 0.26, Ni 3, Cr 1,2, 29
mm diam, bars hardened in oil from 830°C. Izod (2) for steel with 0.25% molybdenum added
Temper brittleness is usually used to describe the notch impact intergranular brittleness (Grain boundaries are
revealed in temper brittle samples by etching in 1 gm cetyl trimethyl ammonium bromide; 20 gm picric acid;
100 cc distilled water, 100 cc ether. Shake mixture, allow to stand for 24 hrs; use portion of top layer and return
to tube afterwards) induced in some steels by slow cooling after tempering above about 600°C and also from
prolonged soaking of tough material between about 400?and 550°C.
Temper brittleness seems to be due to grain boundary enrichment with alloying elements-Mn, Cr, Mo-during

Appendix D. Page 49 of 116.


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austenitising which leads to enhanced segregation of embattling elements P, Sn, Sb, As-by chemical
interaction on slow cooling from 600°C. The return to the tough condition, obtained by rehearing embattled
steel to temperatures above 600°C and rapidly cooling, is due to the redistribution and retention in solution of
the embattling segregation. Antimony (0-001 %), phosphorus (0-008 %), arsenic, tin, manganese increase,
while molybdenum decreases the susceptibility of a steel to embattlement. 0-25 % molybdenum reduces the
brittleness as shown by Izod curve No. 2. Table 1 illustrates the effect rate of cooling after tempering and the
influence of an addition of 0-45 % molybdenum:
Table 1. Steel 0.3% C, 3,5 % Ni, 0.7%, Cr, tempered at 630°C
Cooling TS Izod Izod
Steel Elongation RA
Rate MPa ft lbf J
Ni-Cr Oil 896 18 60 64 87
Ni-Cr Furnance 880 18 60 19 25
Ni-Cr-Mo Furnance 896 18 61 59 80

Appendix D. Page 50 of 116.


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Molybdenum

Molybdenum: A carbide former, prevents brittleness & maintains the steel's strength at high temperatures.
Present in many steels, and air-hardening steels (e.g. A-2, ATS-34) always have 1% or more molybdenum --
molybdenum is what gives those steels the ability to harden in air.

It is Adds greatly to the penetration of hardness and increases toughness of an alloy. It causes steel to resist
softening at high temperatures, which defeats the purpose of forging. If the alloy has below 0.020 percent
molybdenum (Mo), you should be able to forge this alloy with little difficulty.

Molybdenum is used very widely because of its powerful effect in increasing hardenability and also
because in low alloy steels it reduces susceptibility to temper brittleness. It forms stable carbides,
raises the temperature at which softening takes place on tempering and increases resistance to creep.
In high speed steel it can be used to replace approximately twice its weight of tungsten. The corrosion
resistance of stainless steel is improved by molybdenum additions.

Molybdenum increases the hardenability of steel. Molybdenum may produce secondary hardening during the
tempering of quenched steels. It enhances the creep strength of low-alloy steels at elevated temperatures.

Molybdenum substantially increases the resistance to both general and localized corrosion. It increases the
mechanical strength somewhat and strongly promotes a ferritic structure. Molybdenum also promotes the
formation secondary phases in ferritic, ferritic-austenitic and austenitic steels. In martensitic steels it will
increase the hardness at higher tempering temperatures due to its effect on the carbide precipitation.

Molybdenum dissolves in both alpha- and gama-iron and in the presence of carbon forms complex carbides
(FeMo)6C, Fe21Mo2C6, Mo2C. Molybdenum is similar to chromium in its effect on the shape of the TTT-curve
but up to 0.5% appears to be more effective in retarding pearlite and increasing bainite formation. Additions of
0.5% molybdenum have been made to plain carbon steels to give increased strength at boiler temperatures of
400°C, but the element is mainly used in combination with other alloying elements.

Ni-Cr-Mo steels are widely used for ordnance, turbine rotors and other large articles, since molybdenum tends
to minimize temper brittleness and reduces mass effect. Molybdenum is also a constituent in some high-speed
steels, magnet alloys, heat-resisting and corrosion-resisting steels.

Appendix D. Page 51 of 116.


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Vanadium

ƒ Ferrite Promoter.
ƒ Carbide and Nitride Former.

Vanadium acts as a scavenger for oxides, forms vanadium carbide VC, and has a beneficial effect on the
mechanical properties of heat-treated steels, especially in the presence of other elements. It slows up
tempering in the range of 500-600°C and can induce secondary hardening. Chromium-vanadium (0.15%)
steels are used for locomotive forging, automobile axles, coil springs, torsion bars and creep resistance.

Vanadium increases the yield strength and the tensile strength of carbon steel. The addition of small amounts
of Vanadium can significantly increase the strength of steels. Vanadium is one of the primary contributors to
precipitation strengthening in microalloyed steels. When thermomechanical processing TMCP is properly
controlled the ferrite grain size is refined and there is a corresponding increase in toughness. The impact
transition temperature also increases when vanadium is added.

All microalloy steels contain small concentrations of one or more strong carbide and nitride forming
elements. Vanadium, niobium, and titanium combine preferentially with carbon and/or nitrogen to form a fine
dispersion of precipitated particles in the steel matrix.

The presence of vanadium in steel raises the temperature at which grain coarsening sets in and under certain
conditions increases the hardenability. It also lessens softening on tempering and confers secondary hardness
on high speed and other steels. Vanadium carbide is intensely hard and as much as 5% vanadium may be
added to high speed and high chromium tool steel where it improves abrasion resistance. Vanadium is an
important constituent in many types of steel, for widely varying applications, e.g., nitriding, heat-resistance,
tools, wearing plates and other fully hardened parts. In conjunction with molybdenum, vanadium has a marked
effect in enhancing creep resistance.

Vanadium increases the hardness of martensitic steels due to its effect on the type of carbide present. It also
increases tempering resistance. Vanadium stabilises ferrite and will, at high contents, promote ferrite in the
structure. It is only used in hardenable stainless steels.

It retards grain growth within steel even after long exposures at high temperatures, and helps to control grain
structures while heat treating. It is usually present in small quantities of 0.15 to 0.20 percent. Most tool steels
which contain this element seem to absorb shock better that those that do not contain vanadium (V).

Vanadium contributes to wear resistance and hardenability. A carbide former that helps produce fine-grained
steel. A number of steels have vanadium, but M-2, Vascowear, and CPM T440V and 420V (in order of
increasing amounts) have high amounts

Appendix D. Page 52 of 116.


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Tungsten

TUNGSTEN (W): Also known as wolfram, is used as an alloying element in tool steels, as it tends to impart a
tight, small, and dense grain pattern and keen cutting edges when used in relatively small amounts. It will also
cause steel to retain its hardness at higher temperatures and hence will have a detrimental effect upon the
steel's forgeability (otherwise known as "red hard")

Tungsten dissolves in gama-iron and in alpha-iron. With carbon it forms WC and W2C, but in the presence of
iron it forms Fe3W3C or Fe4W2C. A compound with iron, Fe3W2 provides an age-hardening system. Tungsten
raises the critical points in steel and the carbides dissolve slowly over a range of temperature. When
completely dissolved, the tungsten renders transformation sluggish, especially to tempering, and use is made
of this in most hot-working tool ("high speed") and die steels. It Increases wear resistance. When combined
properly with chromium or molybdenum, tungsten will make the steel to be a high-speed steel. The high-speed
steel M-2 has a high amount of tungsten. Tungsten refines the grain size and produces less tendency to
decarburisation during working. Tungsten is also used in magnet, corrosion- and heat-resisting steels.

The effect of the addition of this metal to steel is to increase the strength at normal and elevated
temperatures. Owing to the hardness of tungsten carbide and its influence on secondary hardening,
tungsten is used as the main alloy addition in high speed tool steels, molybdenum being its only
substitute. In addition, tungsten finds considerable application in general tool steels, die and
precipitation hardening steels. It has found a useful application in valves and other steels required for
use at high temperatures. Tungsten is an essential constituent in the sintered hard metals.

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Silicon

ƒ Ferrite Former.
ƒ Encourage Brittleness.

Silicon Si, is one of the principal deoxidizers used in steelmaking. Silicon is less effective than manganese in
increasing as-rolled strength and hardness. In low-carbon steels, silicon is generally detrimental to surface
quality. Silicon increases the resistance to oxidation, both at high temperatures and in strongly oxidising
solutions at lower temperatures. It promotes a ferritic structure.

It has a beneficial effect upon tensile strength and improves hardenability of an alloy. It has a toughening effect
when used in combination with certain other elements. Silicon (Si) is usually added to improve electrical
conductivity of an alloy. Its average concentration is between 1.5 and 2.5 percent.

Silicon is used as a deoxidizer in the manufacture of steel. It slightly increases the strength of ferrite, and when
used in conjunction with other alloys can help increase the toughness and hardness penetration of steel.

Silicon is a powerful deoxidizer, and as such is used in steel making processes in amounts up to about
0·8%. When used as an alloying element, silicon in small percentages will increase the tensile strength
and yield point of structural steels. It is used in amounts of 1·5% to 2% in silicon-manganese spring
steels and ultra-high tensile steels due to its effect in raising the limit of proportionality and resistance
to tempering. Up to 4% in heat resisting steels improves scale resistance owing to the formation of a
protective layer (see also Ihrigizing). The higher the silicon, the higher the temperature at which
protection against further atmospheric oxidation is given. Water vapour and carbon dioxide, however,
attack the layer. Alloys of iron and silicon, containing 15% of the element, are used as acid-resisting
materials, but have the properties of cast irons rather than of steels. Carbon-free alloys with up to 4%
silicon have a high electrical resistance and low hysteresis loss, and are used as transformer steels. In
cast iron, silicon not only serves as a deoxidizer but also has a marked graphitizing effect, thus
improving machinability.

Silicon dissolves in the ferrite, of which it is a fairly effective hardener, and raises the Ac change points and the Ar
points when slowly cooled and also reduces the gama-alpha volume change. Only three types of silicon steel are in
common use-one in conjunction with manganese for springs; the second for electrical purposes, used in sheet form
for the construction of transformer cores, and poles of dynamos and motors, that demand high magnetic
permeability and electrical resistance; and the third is used for automobile valves.

C Si Mn
1. Silico-manganese 0.5 1,5 0.8
2. Silicon steel 0.07 4,3 0.09
3. Silichrome 0.4 3,5 8

It contributes oxidation resistance in heat-resisting steels and is a general purpose deoxidizes.

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Copper

ƒ Austenite Former.
ƒ Impair Forging.
ƒ Use as precipitation hardening alloy e.g17-4PH

Copper dissolves in the ferrite to a limited extent; not more than 3.5% is soluble in steels at normalizing
temperatures, while at room temperature the ferrite is saturated at 0.35%. It lowers the critical points, but
insufficiently to produce martensite by air cooling. The resistance to atmospheric corrosion is improved and
copper steels can be temper hardened.

Copper Cu, in significant amounts is detrimental to hot-working steels. Copper negatively affects forge
welding, but does not seriously affect arc or oxyacetylene welding. Copper can be detrimental to surface
quality. Copper is beneficial to atmospheric corrosion resistance when present in amounts exceeding 0.20%.
Weathering steels are sold having greater than 0.20% Copper.

The addition of about 0.20% copper to low carbon steel may increase its resistance to atmospheric
corrosion by as much as 20% to 30%. In amounts of about 0·50% copper appreciably increases the
tensile and yield strengths. The addition of increasing amounts of copper leads to defects in rolling.
High yield point structural steels containing copper, in association with chromium and appreciable
percentages of silicon and phosphorus have been developed. Copper is also added to some stainless
steels to improve corrosion resistance.

Copper enhances the corrosion resistance in certain acids and promotes an austenitic structure. In
precipitation hardening steels copper is used to form the intermetallic compounds that are used to increase the
strength.

Phosphorous

ƒ Embrittlement Effects
ƒ Increase Machinability.
ƒ Undesirable Element.

Phosphorus P, increases strength and hardness and decreases ductility and notch impact toughness of
steel. The adverse effects on ductility and toughness are greater in quenched and tempered higher-carbon
steels. Phosphorous levels are normally controlled to low levels. Higher phosphorus is specified in
low-carbon free-machining steels to improve machinability.

Although it has been used to increase the tensile strength of steel and to improve resistance to
atmospheric corrosion, phosphorus is usually regarded as an undesirable impurity because of its
embrittling effect. In most British specifications the maximum permitted is 0.05 %, but in steel for

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nitriding it may be restricted to a maximum of 0·02 % since during the nitriding treatment phosphorus
has a temper embrittling effect.

Sulphur

ƒ Increase Machinability.
ƒ Undesirable element.
ƒ Embrittlement Effects.
ƒ Impair Ductility.
ƒ Impair Weldability.

SULFUR S, Is usually regarded as an impurity in most alloys and its addition to steel is held to a minimum as it
is damaging to the hot forming characteristics of steel. It is, however added to increase machinability. A
word of caution, some alloys are offered in different forms, an example is E52100. This particular steel
can be had in either a "Bearing Quality" or "Machining Quality" the latter having sulfur added to increase
machinability.

Sulfur decreases ductility and notch impact toughness especially in the transverse direction. Weldability
decreases with increasing sulfur content. Sulfur is found primarily in the form of sulfide inclusions. Sulfur
levels are normally controlled to low levels. The only exception is free-machining steels, where sulfur is added
to improve machinability.

A non-metal, which combines with iron to form iron sulphides, in which form its effect is to make the
steel red short but combined with manganese its influence is less injurious. In steel the sulphur content
is usually specified as less than 0.05 % but it may be added deliberately to improve machinability.

Sulphur is added to certain stainless steels, the free-machining grades, in order to increase the machinability.
At the levels present in these grades sulphur will substantially reduce corrosion resistance, ductility and
fabrication properties, such as weldability and formability.

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Lead

ƒ Improve Machinability.
ƒ Undesirable Element.
ƒ Impair Ductility.
ƒ Impair Toughness.
ƒ Impair Creep Strength.

Lead Pb, increase the machinability of steel and has no effect upon the other properties of the metal. Lead is
virtually insoluble in liquid or solid steel. However, lead is sometimes added to carbon and alloy steels by
means of mechanical dispersion during pouring to improve the machinability.

The addition of about 025% lead improves machinability. It also causes a reduction in fatigue strength,
ductility and toughness but this only becomes serious in the transverse direction and at high tensile
levels. In creep resisting alloys very small amounts of lead may be harmful.

Hydrogen

Hydrogen H, in steel is an undesirable impurity which is introduced from moisture in the atmosphere or
the charge during melting. If a large amount of hydrogen is present in the liquid steel, some may be
liberated on freezing giving an unsound ingot, evolution of hydrogen subsequently when the solid steel
cools may cause hair line cracks. Hydrogen can be reduced to safe proportions by casting in vacuum
or by prolonged annealing. It may also be introduced into steel by electrolytic action or by pickling and
may then cause brittleness.

Selenium

Selenium Se, A metalloid closely resembling sulphur in its properties. It is sometimes added to steels
to the extent of 0·2 % to 0·3 % to improve machinability.

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Tantalum

Tantalum Ta, This metal is associated with niobium and is very similar to it chemically. As an alloying
addition to steel, niobium is preferred.

Tellurium is added to steel either alone or together with selenium to promote machinability. It is a
powerful carbide stabilizer and has been also added to cast iron where it is said to increase the depth
of chill and to prevent shrinkage. It may be added in small amounts to the molten iron or by the use of
cores dipped or painted with washes containing tellurium in suspension.

Tin

Tin Sn, Owing to its good resistance to corrosion in many conditions, the major use of tin is in the form
of coatings for steel and copper alloys. It is an undesirable impurity in steel giving rise to temper
brittleness, but is less harmful than phosphorus.

Calcium

Calcium Ca, This metal in the form of calcium silicide is sometimes added to steel as a deoxidizer and
degasefier.

Cerium

Cerium Ce, a metal of the rare earth class which in many respects resemble the alkali metals. The hot
working properties of high alloy corrosion- and heat-resistant steels maybe improved by the addition of
cerium, whilst in cast iron, cerium acts as a deoxidizer and desulphurizer but when the sulphur content
has been reduced to a value of about 0·015%, the cerium enters into solution in the cast iron and
functions as a powerful carbide stabilizer. In amounts above 0·02%, cerium is the operative factor in
the production of nodular graphite structures in cast iron.

Cerium is one of the rare earth metals (REM) and is added in small amounts to certain heat resistant
temperature steels and alloys in order to increase the resistance to oxidation and high temperature corrosion.

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Nitrogen

Nitrogen N, Nitrogen can combine with many metals to form nitrides and is thus applied to the case
hardening of steel, the usual source for this purpose being ammonia. The incorporation of nitrogen in
austenitic chromium-nickel steels stabilizes the austenite and increases the strength. In carbon steels it
has an influence on creep. (See Abnormal Steels)

Nitrogen is a very strong austenite former and strongly promotes an austenitic structure. It also substantially
increases the mechanical strength. Nitrogen increases the resistance to localised corrosion, especially in
combination with molybdenum. In ferritic stainless steels nitrogen will strongly reduce toughness and corrosion
resistance. In the martensitic and martensitic-austenitic steels nitrogen increases both hardness and strength
but reduces the toughness.

Boron

Boron B, is added to fully killed steel to improve hardenability. Boron-treated steels are produced to a range of
0.0005 to 0.003%. Whenever boron is substituted in part for other alloys, it should be done only with
hardenability in mind because the lowered alloy content may be harmful for some applications.

The addition of about 0.003 % of boron confers increased harden ability to steels in the quenched and
tempered condition. Further, it has been found that the addition of 0·003% boron to low carbon, 0·50%
molybdenum steel in the normalized condition doubles the yield strength and gives a 30% increase in
tensile strength, but the advantage due to boron is very slight when molybdenum is less than 0.35%
causes difficulty in forging. As much as 2% may be added to steels used in nuclear engineering.

Boron is a potent alloying element in steel. A very small amount of boron (about 0.001%) has a strong effect
on hardenability. Boron steels are generally produced within a range of 0.0005 to 0.003%. Boron is most
effective in lower carbon steels.

Boron. In recent years, especially in USA, 0.003-0.005% boron has been added to previously fully killed,
fine-grain steel to increase the hardenability of the steel. The yield ratio and impact are definitely improved,
provided advantage is taken of the increased hardenability obtained and the steel is fully hardened before
tempering. In conjunction with molybdenum boron forms a useful group of high tensile bainitic steels. Boron is
used in some hard facing alloys and for nuclear control rods.

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Aluminium

Aluminum Al, is widely used as a deoxidizer. Aluminum can control austenite grain growth in reheated steels
and is therefore added to control grain size. Aluminum is the most effective alloy in controlling grain growth
prior to quenching. Titanium, zirconium, and vanadium are also valuable grain growth inhibitors, but there
carbides are difficult to dissolve into solution in austenite.

As a deoxidizer, up to 0.05% aluminum may be added to steel. For increasing fine grain characteristics
or sub-zero impact properties, up to 0·10% may be added. Nitriding steels contain about 1% aluminum
for promoting a high surface hardness when heated in ammonia. Still larger additions made to heat
resisting steels promote resistance to scaling. Approximately 5% added to chromium steel increases
electrical resistivity.

Aluminium improves oxidation resistance, if added in substantial amounts. It is used in certain heat resistant
alloys for this purpose. In precipitation hardening steels aluminium is used to form the intermetallic compounds
that increase the strength in the aged condition.

Zirconium

Zirconium Zr, can be added to killed high-strength low-alloy steels to achieve improvements in inclusion
characteristics. Zirconium causes sulfide inclusions to be globular rather than elongated thus improving
toughness and ductility in transverse bending.

Zirconium acts as a deoxidizing element in steel and combines with the sulphur.

Niobium

Niobium Nb (Columbium) increases the yield strength and, to a lesser degree, the tensile strength of carbon
steel. The addition of small amounts of Niobium can significantly increase the yield strength of
steels. Niobium can also have a moderate precipitation strengthening effect. Its main contributions are to form
precipitates above the transformation temperature, and to retard the recrystallization of austenite, thus
promoting a fine-grain microstructure having improved strength and toughness.

The metal is also known as columbium. It occurs in association with tantalum, to which it is closely
related. Niobium is a strong carbide-forming element and as such is added to certain austenitic
corrosion-resistant steels of the 18/8 chromium-nickel type for the prevention of intercrystalline
corrosion. Where niobium is used as the stabilizer, it is usually specified that it should be present in an
amount at least 8 times that of the carbon content. Further, niobium is often used as a constituent of
the electrodes used in the welding of such steels. Niobium is added to heat-resisting steels and

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enhances creep strength. In small amounts, of the order of 0·05%, it increases the yield strength of
mild steel.

Niobium is both a strong ferrite and carbide former. As titanium it promotes a ferritic structure. In austenitic
steels it is added to improve the resistance to intergranular corrosion but it also enhances mechanical
properties at high temperatures. In martensitic steels niobium lowers the hardness and increases the
tempering resistance. In U.S. it is also referred to as Columbium (Cb).

Titanium

Titanium Ti, is used to retard grain growth and thus improve toughness. Titanium is also used to achieve
improvements in inclusion characteristics. Titanium causes sulfide inclusions to be globular rather than
elongated thus improving toughness and ductility in transverse bending.

Titanium is a strong ferrite former and a strong carbide former, thus lowering the effective carbon content and
promoting a ferritic structure in two ways. In austenitic steels it is added to increase the resistance to
intergranular corrosion but it also increases the mechanical properties at high temperatures. In ferritic stainless
steels titanium is added to improve toughness and corrosion resistance by lowering the amount of interstitials
in solid solution. In martensitic steels titanium lowers the martensite hardness and increases the tempering
resistance. In precipitation hardening steels titanium is used to form the intermetallic compounds that are used
to increase the strength.

The principal use of titanium is to stabilize carbon by forming titanium carbide. In austenitic stainless
steels it is used in this way to prevent inter crystalline corrosion, the titanium addition being at least four
times the carbon content. It is also added to low carbon steels to prevent blistering during vitreous
enameling. Titanium carbide is used with tungsten carbide in the manufacture of hard metal tools.

Cobalt

Cobalt Co, Increases strength and hardness, permits quenching at higher temperatures. In some
steels used for nuclear engineering cobalt is an undesirable impurity, even in amounts as small as
0·02%. Unlike most other alloying elements cobalt reduces hardenability. It raises the red hardness of
steel and this is the reason for adding 5% to 10% cobalt to certain types of high speed steels,
developed for the specific purpose of cutting exceptionally hard materials. Heat resisting alloys with
high cobalt contents have been developed for use in gas turbines. Cobalt is added to the extent of up
to 40 % to magnet steels requiring high coercive force and it is used in electrical- resistance alloys. In
the sintered hard metals Cobalt acts as the binding metal.

Cobalt only used as an alloying element in martensitic steels where it increases the hardness and tempering
resistance, especially at higher temperatures.

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Cobalt has a high solubility in alpha- and gama-iron but a weak carbide-forming tendency. It decreases
hardenability but sustains hardness during tempering. It is used in "Stellite" type alloys, gas turbine steel,
magnets and as a bond in hard metal.

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Carbon content, steel classifications, and alloy steels

Generally, carbon is the most important commercial steel alloy. Increasing carbon content increases hardness
and strength and improves hardenability. But carbon also increases brittleness and reduces weldability
because of its tendency to form martensite. This means carbon content can be both a blessing and a curse
when it comes to commercial steel.

And while there are steels that have up to 2 percent carbon content, they are the exception. Most steel
contains less than 0.35 percent carbon. To put this in perspective, keep in mind that’s 35/100 of 1 percent.

Now, any steel in the 0.35 to 1.86 percent carbon content range can be hardened using a heat-quench-temper
cycle. Most commercial steels are classified into one of three groups:
1. Plain carbon steels
2. Low-alloy steels
3. High-alloy steels

Plain Carbon Steels

These steels usually are iron with less than 1 percent carbon, plus small amounts of manganese, phosphorus,
sulfur, and silicon. The weldability and other characteristics of these steels are primarily a product of carbon
content, although the alloying and residual elements do have a minor influence.

Plain carbon steels are further subdivided into four groups:


1. Low
2. Medium
3. High
4. Very high

Low. Often called mild steels, low-carbon steels have less than 0.30 percent carbon and are the most
commonly used grades. They machine and weld nicely and are more ductile than higher-carbon steels.

Medium. Medium-carbon steels have from 0.30 to 0.45 percent carbon. Increased carbon means increased
hardness and tensile strength, decreased ductility, and more difficult machining.

High. With 0.45 to 0.75 percent carbon, these steels can be challenging to weld. Preheating, postheating (to
control cooling rate), and sometimes even heating during welding become necessary to produce acceptable
welds and to control the mechanical properties of the steel after welding.

Very High. With up to 1.50 percent carbon content, very high-carbon steels are used for hard steel products
such as metal cutting tools and truck springs. Like high-carbon steels, they require heat treating before, during,
and after welding to maintain their mechanical properties.

Low-alloy Steels

When these steels are designed for welded applications, their carbon content is usually below 0.25 percent
and often below 0.15 percent. Typical alloys include nickel, chromium, molybdenum, manganese, and silicon,
which add strength at room temperatures and increase low-temperature notch toughness.

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These alloys can, in the right combination, improve corrosion resistance and influence the steel’s response to
heat treatment. But the alloys added can also negatively influence crack susceptibility, so it’s a good idea to
use low-hydrogen welding processes with them. Preheating might also prove necessary. This can be
determined by using the carbon equivalent formula, which we’ll cover in a later issue.

High-alloy Steels

For the most part, we’re talking about stainless steel here, the most important commercial high-alloy steel.
Stainless steels are at least 12 percent chromium and many have high nickel contents. The three basic types
of stainless are:
1. Austenitic
2. Ferritic
3. Martensitic

Martensitic stainless steels make up the cutlery grades. They have the least amount of chromium, offer high
hardenability, and require both pre- and postheating when welding to prevent cracking in the heat-affected
zone (HAZ).

Ferritic stainless steels have 12 to 27 percent chromium with small amounts of austenite-forming alloys.

Austenitic stainless steels offer excellent weldability, but austenite isn’t stable at room temperature.
Consequently, specific alloys must be added to stabilize austenite. The most important austenite stabilizer is
nickel, and others include carbon, manganese, and nitrogen.

Special properties, including corrosion resistance, oxidation resistance, and strength at high temperatures, can
be incorporated into austenitic stainless steels by adding certain alloys like chromium, nickel, molybdenum,
nitrogen, titanium, and columbium. And while carbon can add strength at high temperatures, it can also reduce
corrosion resistance by forming a compound with chromium. It’s important to note that austenitic alloys can’t
be hardened by heat treatment. That means they don’t harden in the welding HAZ.

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* Stainless steels always have a high chromium content, often considerable amounts of nickel, and sometimes contain

molybdenum and other elements. Stainless steels are identified by a three-digit number beginning with 2, 3, 4, or 5.

Figure 1

Be sure to check the appropriate AISI and SAE publications for the latest revisions.

Steel Classification Systems

Before we look at a couple of common steel classification systems, let’s consider one more high-carbon metal,
cast iron. The carbon content of cast iron is 2.1 percent or more. There are four basic types of cast iron:

1. Gray cast iron, which is relatively soft. It’s easily machined and welded, and you’ll find it used for
engine cylinder blocks, pipe, and machine tool structures.

2. White cast iron, which is hard, brittle, and not weldable. It has a compressive strength of more than
200.000 pounds per square inch (PSI), and when it’s annealed, it becomes malleable cast iron.

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3. Malleable cast iron, which is annealed white cast iron. It can be welded, machined, is ductile, and
offers good strength and shock resistance.

4. Ductile cast iron, which is sometimes called nodular or spheroidal graphite cast iron. It gets this name
because its carbon is in the shape of small spheres, not flakes. This makes it both ductile and
malleable. It’s also weldable.

Now let’s take a look at a typical steel classification system (see Figure 1). Both the Society of Automotive
Engineers (SAE) and the American Iron and Steel Institute (AISI) use virtually identical systems. Both are
based on a four-digit system with the first number usually indicating the basic type of steel and the first two
numbers together indicating the series within the basic alloy group.

Keep in mind there may be a number of series within a basic alloy group, depending on the amount of the
principal alloying elements. The last two or three numbers refer to the approximate permissible range of
carbon content in points (hundredths of a percent).

These classification systems can become fairly complex, and Figure 1 is just a basic representation. Be sure to
reference the most recent AISI and SAE publications for the latest revisions.

That’s a look at some basics concerning the iron-carbon-steel relationship and its influences on welding and
metal alloys. Next time we’ll look at hardening and ways to make metals stronger. We’ll also consider the
influences of some key alloying elements and the effects of welding on metallurgy.

Carbon Steel

Carbon steels and alloy steels are designated by a four digit number, where the first two digits indicate the alloying
elements and the last two digits indicate the amount of carbon, in hundredths of a percent by weight. For example,
a 1060 steel is a plain carbon steel containing 0.60 wt% C.
designation Type

Carbon steels

10xx Plain carbon (Mn 1.00% max)

11xx Resulfurized

12xx Resulfurized and rephosphorized

15xx Plain carbon (Mn 1.00% to 1.65%)

Manganese steels

13xx Mn 1.75%

Nickel steels

23xx Ni 3.50%

25xx Ni 5.00%

Nickel-chromium steels

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31xx Ni 1.25%, Cr 0.65% or 0.80%

32xx Ni 1.25%, Cr 1.07%

33xx Ni 3.50%, Cr 1.50% or 1.57%

34xx Ni 3.00%, Cr 0.77%

Molybdenum steels

40xx Mo 0.20% or 0.25% or 0.25% Mo & 0.042 S

44xx Mo 0.40% or 0.52%

Chromium-molybdenum (Chromoly) steels

41xx Cr 0.50% or 0.80% or 0.95%, Mo 0.12% or 0.20% or 0.25% or 0.30%

Nickel-chromium-molybdenum steels

43xx Ni 1.82%, Cr 0.50% to 0.80%, Mo 0.25%

43BVxx Ni 1.82%, Cr 0.50%, Mo 0.12% or 0.35%, V 0.03% min

47xx Ni 1.05%, Cr 0.45%, Mo 0.20% or 0.35%

81xx Ni 0.30%, Cr 0.40%, Mo 0.12%

81Bxx Ni 0.30%, Cr 0.45%, Mo 0.12%

86xx Ni 0.55%, Cr 0.50%, Mo 0.20%

87xx Ni 0.55%, Cr 0.50%, Mo 0.25%

88xx Ni 0.55%, Cr 0.50%, Mo 0.35%

93xx Ni 3.25%, Cr 1.20%, Mo 0.12%

94xx Ni 0.45%, Cr 0.40%, Mo 0.12%

97xx Ni 0.55%, Cr 0.20%, Mo 0.20%

98xx Ni 1.00%, Cr 0.80%, Mo 0.25%

Nickel-molybdenum steels

46xx Ni 0.85% or 1.82%, Mo 0.20% or 0.25%

48xx Ni 3.50%, Mo 0.25%

Chromium steels

50xx Cr 0.27% or 0.40% or 0.50% or 0.65%

50xxx Cr 0.50%, C 1.00% min

50Bxx Cr 0.28% or 0.50%

51xx Cr 0.80% or 0.87% or 0.92% or 1.00% or 1.05%

51xxx Cr 1.02%, C 1.00% min

51Bxx Cr 0.80%

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52xxx Cr 1.45%, C 1.00% min

Chromium-vanadium steels

61xx Cr 0.60% or 0.80% or 0.95%, V 0.10% or 0.15% min

Tungsten-chromium steels

72xx W 1.75%, Cr 0.75%

Silicon-manganese steels

92xx Si 1.40% or 2.00%, Mn 0.65% or 0.82% or 0.85%, Cr 0.00% or 0.65%

High-strength low-alloy steels

9xx Various SAE grades

xxBxx Boron steels

xxLxx Leaded steels

Stainless steel

ƒ 200 Series: austenitic chromium-nickel-manganese alloys


ƒ 300 Series: austenitic chromium-nickel alloys
ƒ Type 301: highly ductile, for formed products. Also hardens rapidly during mechanical working.
ƒ Type 303: free machining version of 304 via addition of sulfur
ƒ Type 304: the most common; the classic 18/8 stainless steel.
ƒ Type 316: the next most common; for food and surgical stainless steel uses; alloy addition of
molybdenum prevents specific forms of corrosion. 316 steel is more resistant to corrosion than
18-8 stainless steels. 316 steel is used in the handling of certain food and pharmaceutical
products where it is often required in order to minimize metallic contamination. 316 steel is also
known as "marine grade" stainless steel due to its increased ability to resist saltwater corrosion
compared to type 304. SS316 is often used for building nuclear reprocessing plants.
ƒ 400 Series: ferritic and martensitic chromium alloys
ƒ Type 408: heat-resistant; poor corrosion resistance; 11% chromium, 8% nickel.
ƒ Type 409: cheapest type; used for automobile exhausts; ferritic (iron/chromium only).
ƒ Type 410: martensitic (high-strength iron/chromium).
ƒ Type 416: the most machinable stainless steel; achieved by the addition of extra sulfur which
reduces corrosion resistance. Often used for "stainless" rifle barrels
ƒ Type 420: "Cutlery grade" martensitic; similar to the Brearley's original "rustless steel". Also
known as "surgical steel".
ƒ Type 430: decorative, e.g., for automotive trim; ferritic.
ƒ Type 440: a higher grade of cutlery steel, with more carbon in it, which allows for much better
edge retention when the steel is heat treated properly.
ƒ 500 Series: heat resisting chromium alloys
ƒ 600 Series: martensitic precipitation hardening alloys

Appendix D. Page 68 of 116.


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ƒ Type 630: most common PH stainless, better known as 17-4; 17% chromium, 4% nickel

Stainless steel designations

SAE UNS
% Cr % Ni %C % Mn % Si %P %S %N Other
designation designation

Austenitic

201 S20100 16–18 3.5–5.5 0.15 5.5–7.5 0.75 0.06 0.03 0.25 -

202 S20200 17–19 4–6 0.15 7.5–10.0 0.75 0.06 0.03 0.25 -

205 S20500 16.5–18 1–1.75 0.12–0.25 14–15.5 0.75 0.06 0.03 0.32–0.40 -

301 S30100 16–18 6–8 0.15 2 0.75 0.045 0.03 - -

302 S30200 17–19 8–10 0.15 2 0.75 0.045 0.03 0.1 -

302B S30215 17–19 8–10 0.15 2 2.0–3.0 0.045 0.03 - -

0.15 Mo 0.60
303 S30300 17–19 8–10 0.15 2 1 0.2 -
min (optional)

303Se S30323 17–19 8–10 0.15 2 1 0.2 0.06 - 0.15 Se min

304 S30400 18–20 8–10.50 0.08 2 0.75 0.045 0.03 0.1 -

304L S30403 18–20 8–12 0.03 2 0.75 0.045 0.03 0.1 -

304Cu S30430 17–19 8–10 0.08 2 0.75 0.045 0.03 - 3–4 Cu

304N S30451 18–20 8–10.50 0.08 2 0.75 0.045 0.03 0.10–0.16 -

305 S30500 17–19 10.50–13 0.12 2 0.75 0.045 0.03 - -

308 S30800 19–21 10–12 0.08 2 1 0.045 0.03 - -

309 S30900 22–24 12–15 0.2 2 1 0.045 0.03 - -

309S S30908 22–24 12–15 0.08 2 1 0.045 0.03 - -

310 S31000 24–26 19–22 0.25 2 1.5 0.045 0.03 - -

310S S31008 24–26 19–22 0.08 2 1.5 0.045 0.03 - -

314 S31400 23–26 19–22 0.25 2 1.5–3.0 0.045 0.03 - -

316 S31600 16–18 10–14 0.08 2 0.75 0.045 0.03 0.10 2.0–3.0 Mo

316L S31603 16–18 10–14 0.03 2 0.75 0.045 0.03 0.10 2.0–3.0 Mo

0.10
316F S31620 16–18 10–14 0.08 2 1 0.2 - 1.75–2.50 Mo
min

316N S31651 16–18 10–14 0.08 2 0.75 0.045 0.03 0.10–0.16 2.0–3.0 Mo

317 S31700 18–20 11–15 0.08 2 0.75 0.045 0.03 0.10 max 3.0–4.0 Mo

317L S31703 18–20 11–15 0.03 2 0.75 0.045 0.03 0.10 max 3.0–4.0 Mo

Appendix D. Page 69 of 116.


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Ti 5(C+N)
321 S32100 17–19 9–12 0.08 2 0.75 0.045 0.03 0.10 max
min, 0.70 max

329 S32900 23–28 2.5–5 0.08 2 0.75 0.04 0.03 - 1–2 Mo

330 N08330 17–20 34–37 0.08 2 0.75–1.50 0.04 0.03 - -

Nb + Ta, 10 x
347 S34700 17–19 9–13 0.08 2 0.75 0.045 0.030 -
C min, 1 max

Nb + Ta, 10 x
C min, 1 max,
348 S34800 17–19 9–13 0.08 2 0.75 0.045 0.030 -
but 0.10 Ta
max; 0.20 Ca

384 S38400 15–17 17–19 0.08 2 1 0.045 0.03 - -

Ferritic

0.1–0.3 Al,
405 S40500 11.5–14.5 - 0.08 1 1 0.04 0.03 -
0.60 max

Ti 6 x C, but
409 S40900 10.5–11.75 0.05 0.08 1 1 0.045 0.03 -
0.75 max

429 S42900 14–16 0.75 0.12 1 1 0.04 0.03 - -

430 S43000 16–18 0.75 0.12 1 1 0.04 0.03 - -

0.15 0.60 Mo
430F S43020 16–18 - 0.12 1.25 1 0.06 -
min (optional)

430FSe S43023 16–18 - 0.12 1.25 1 0.06 0.06 - 0.15 Se min

434 S43400 16–18 - 0.12 1 1 0.04 0.03 - 0.75–1.25 Mo

0.75–1.25
Mo; Nb+Ta 5
436 S43600 16–18 - 0.12 1 1 0.04 0.03 -
x C min, 0.70
max

442 S44200 18–23 - 0.2 1 1 0.04 0.03 - -

446 S44600 23–27 0.25 0.2 1.5 1 0.04 0.03 - -

Martensitic

403 S40300 11.5–13.0 0.60 0.15 1 0.5 0.04 0.03 - -

410 S41000 11.5–13.5 0.75 0.15 1 1 0.04 0.03 - -

414 S41400 11.5–13.5 1.25–2.50 0.15 1 1 0.04 0.03 - -

0.15 0.060 Mo
416 S41600 12–14 - 0.15 1.25 1 0.06 -
min (optional)

416Se S41623 12–14 - 0.15 1.25 1 0.06 0.06 - 0.15 Se min

Appendix D. Page 70 of 116.


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420 S42000 12–14 - 0.15 min 1 1 0.04 0.03 - -

0.15 0.60 Mo max


420F S42020 12–14 - 0.15 min 1.25 1 0.06 -
min (optional)

0.90–1.25
Mo;
422 S42200 11.0–12.5 0.50–1.0 0.20–0.25 0.5–1.0 0.5 0.025 0.025 -
0.20–0.30 V;
0.90–1.25 W

431 S41623 15–17 1.25–2.50 0.2 1 1 0.04 0.03 - -

440A S44002 16–18 - 0.60–0.75 1 1 0.04 0.03 - 0.75 Mo

440B S44003 16–18 - 0.75–0.95 1 1 0.04 0.03 - 0.75 Mo

440C S44004 16–18 - 0.95–1.20 1 1 0.04 0.03 - 0.75 Mo

Heat resisting

501 S50100 4–6 - 0.10 min 1 1 0.04 0.03 - 0.40–0.65 Mo

502 S50200 4–6 - 0.1 1 1 0.04 0.03 - 0.40–0.65 Mo

Unified numbering system

Introduction to the Unified Numbering System of Ferrous Metals and Alloys


http://www.key-to-steel.com/Articles/Art111.htm
http://en.wikipedia.org/wiki/Unified_numbering_system

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Strength in Steel

Strength in steels arises from several phenomena, which usually contribute collectively to the observed mechanical
properties. The heat treatment of steels is aimed at adjusting these contributions so that the required balance of
mechanical properties is achieved. Fortunately the γ/α phase change allows great variations in microstructure to be
produced, so that a wide range of mechanical properties can be obtained even in plain carbon steels. The additional
use of metallic alloying elements, primarily as a result of their influence on the transformation, provides an even
greater control over microstructure, with consequent benefits in the mechanical properties

The simplest version of analyzes the effects of alloying elements on iron-carbon alloys would require analysis of
a large number of ternary alloy diagrams over a wide temperature range. However, Wever pointed out that iron
binary equilibrium systems fall into four main categories (Fig. 1): open and closed γ-field systems, and expanded
and contracted γ-field systems. This approach indicates that alloying elements can influence the equilibrium
diagram in two ways:
by expanding the γ-field, and encouraging the formation of austenite over wider compositional limits. These
elements are called γ-stabilizers.
by contracting the γ-field, and encouraging the formation of ferrite over wider compositional limits. These
elements are called α-stabilizers.
The form of the diagram depends to some degree on the electronic structure of the alloying elements which is
reflected in their relative positions in the periodic classification.

Class 1: open γ-field. To this group belong the important steel alloying elements nickel and manganese, as well
as cobalt and the inert metals ruthenium, rhodium, palladium, osmium, iridium and platinum. Both nickel and
manganese, if added in sufficiently high concentration, completely eliminate the bcc α-iron phase and replace it,
down to room temperature, with the γ-phase. So nickel and manganese depress the phase transformation from γ
to α to lower temperatures (Fig. 1a), i.e. both Ac1 and Ac3 are lowered. It is also easier to obtain metastable
austenite by quenching from the γ-region to room temperature, consequently nickel and manganese are useful
elements in the formulation of austenitic steels.
Class 2: expanded γ-field. Carbon and nitrogen are the most important elements in this group. The γ-phase field
is expanded, but its range of existence is cut short by compound formation (Fig.1b). Copper, zinc and gold have
a similar influence. The expansion of the γ-field by carbon, and nitrogen, underlies the whole of the heat
treatment of steels, by allowing formation of a homogeneous solid solution (austenite) containing up to 2.0 wt %
of carbon or 2.8 wt % of nitrogen.
Class 3: closed γ-field. Many elements restrict the formation of γ-iron, causing the γ-area of the diagram to
contract to a small area referred to as the gamma loop (Fig. 1c). This means that the relevant elements are
encouraging the formation of bcc iron (ferrite), and one result is that the δ- and γ-phase fields become
continuous. Alloys in which this has taken place are, therefore, not amenable to the normal heat treatments
involving cooling through the γ/α-phase transformation. Silicon, aluminium, beryllium and phosphorus fall into
this category, together with the strong carbide forming elements, titanium, vanadium, molybdenum and

Appendix D. Page 72 of 116.


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chromium.

Figure 1. Classification of iron alloy phase diagrams: a. open γ-field; b. expanded γ-field; c. closed γ-field

Class 4: contracted y-field. Boron is the most significant element of this group, together with the carbide forming
elements tantalum, niobium and zirconium. The γ-loop is strongly contracted, but is accompanied by compound

Appendix D. Page 73 of 116.


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formation (Fig. 1d).


The distribution of alloying elements in steels. Although only binary systems have been considered so far, when
carbon is included to make ternary systems the same general principles usually apply. For a fixed carbon content,
as the alloying clement is added the y-field is either expanded or contracted depending on the particular solute.
With an element such as silicon the γ-field is restricted and there is a corresponding enlargement of the α-field. If
vanadium is added, the γ-field is contracted and there will be vanadium carbide in equilibrium with ferrite over
much of the ferrite field. Nickel does not form a carbide and expands the γ-field. Normally elements with
opposing tendencies will cancel each other out at the appropriate combinations, but in some cases anomalies
occur. For example, chromium added to nickel in a steel in concentrations around 18% helps to stabilize the
γ-phase, as shown by 18Cr8Ni austenitic steels.
One convenient way of illustrating quantitatively the effect of an alloying element on the γ-phase field of the Fe-C
system is to project on to the Fe-C plane of the ternary system the γ-phase field boundaries for increasing
concentration of a particular alloying element. For more precise and extensive information, it is necessary to
consider series of isothermal sections in true ternary systems Fe-C-X, but even in some of the more familiar
systems the full information is not available, partly because the acquisition of accurate data can be a difficult and
very time-consuming process.
Recently the introduction of computer-based methods has permitted the synthesis of extensive thermochemical
and phase equilibria data, and its presentation in the form, for example, of isothermal sections over a wide range
of temperatures.
If only steels in which the austenite transforms to ferrite and carbide on slow cooling are considered, the alloying
elements can be divided into three categories:
elements which enter only the ferrite phase
elements which form stable carbides and also enter the ferrite phase
elements which enter only the carbide phase.
In the first category there are elements such as nickel, copper, phosphorus and silicon which, in transformable
steels, are normally found in solid solution in the ferrite phase, their solubility in cementite or in alloy carbides
being quite low.
The majority of alloying elements used in steels fall into the second category, in so far as they are carbide
formers and as such, at low concentrations, go into solid solution in cementite, but will also form solid solutions in
ferrite. At higher concentrations most will form alloy carbides, which are thermodynamically more stable than
cementite.
Typical examples are manganese, chromium, molybdenum, vanadium, titanium, tungsten and niobium.
Manganese carbide is not found in steels, but instead manganese enters readily into solid solution in Fe3C. The
carbide-forming elements are usually present greatly in excess of the amounts needed in the carbide phase,
which are determined primarily by the carbon content of the steel. The remainder enters into solid solution in the
ferrite with the non-carbide forming elements nickel and silicon. Some of these elements, notably titanium,
tungsten, and molybdenum, produce substantial solid solution hardening of ferrite.
In the third category there are a few elements which enter predominantly the carbide phase. Nitrogen is the most
important element and it forms carbo-nitrides with iron and many alloying elements. However, in the presence of
certain very strong nitride forming elements, e.g. titanium and aluminum, separate alloy nitride phases can occur.
While ternary phase diagrams, Fe-C-X, can be particularly helpful in understanding the phases which can exist in
simple steels, isothermal sections for a number of temperatures are needed before an adequate picture of the
equilibrium phases can be built up. For more complex steels the task is formidable and equilibrium diagrams can

Appendix D. Page 74 of 116.


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only give a rough guide to the structures likely to be encountered. It is, however, possible to construct
pseudobinary diagrams for groups of steels, which give an overall view of the equilibrium phases likely to be
encountered at a particular temperature.
Structural changes resulting from alloying additions. The addition to iron-carbon alloys of elements such as nickel,
silicon, manganese, which do not form carbides in competition with cementite, does not basically alter the
microstructures formed after transformation. However, in the case of strong carbide-forming elements such as
molybdenum, chromium and tungsten, cementite will be replaced by the appropriate alloy carbides, often at
relatively low alloying element concentrations. Still stronger carbide forming elements such as niobium, titanium
and vanadium are capable of forming alloy carbides, preferentially at alloying concentrations less than 0.1 wt%.
It would, therefore, be expected that the microstructures of steels containing these elements would be radically
altered. It has been shown how the difference in solubility of carbon in austenite and ferrite leads to the familiar
ferrite/cementite aggregates in plain carbon steels. This means that, because the solubility of cementite in
austenite is much greater than in ferrite, it is possible to redistribute the cementite by holding the steel in the
austenite region to take it into solution, and then allowing transformation to take place to ferrite and cementite.
Examining the possible alloy carbides, and nitrides, in the same way, shows that all the familiar ones are much
less soluble in austenite than is cementite.
Chromium and molybdenum carbides are not included, but they are substantially more soluble in austenite than
the other carbides. Detailed consideration of such data, together with practical knowledge of alloy steel behavior,
indicates that, for niobium and titanium, concentrations of greater than about 0.25 wt % will form excess alloy
carbides which cannot be dissolved in austenite at the highest solution temperatures. With vanadium the limit is
higher at 1-2%, and with molybdenum up to about 5%. Chromium has a much higher limit before complete
solution of chromium carbide in austenite becomes difficult. This argument assumes that sufficient carbon is
present in the steel to combine with the alloying element. If not, the excess metallic element will go into solid
solution both in the austenite and the ferrite.
In general, the fibrous morphology represents a closer approach to an equilibrium structure so it is more
predominant in steels which have transformed slowly. In contrast, the interphase precipitation and dislocation
nucleated structures occur more readily in rapidly transforming steels, where there is a high driving force, for
example, in microalloyed steels.
The clearest analogy with pearlite is found when the alloy carbide in lath morphology forms nodules in
association with ferrite. These pearlitic nodules are often encountered at temperatures just below Ac1, in steels
which transform relatively slowly.
For example, these structures are obtained in chromium steels with between 4% and 12% chromium and the
crystallography is analogous to that of cementitic pearlite. It is, however, different in detail because of the
different crystal structures of the possible carbides. The structures observed are relatively coarse, but finer than
pearlite formed under equivalent conditions, because of the need for the partition of the alloying element, e.g.
chromium between the carbide and the ferrite. To achieve this, the interlamellar spacing must be substantially
finer than in the equivalent iron-carbon case.
Interphase precipitation. Interphase precipitation has been shown to nucleate periodically at the γ/α interface
during the transformation. The precipitate particles form in bands which are closely parallel to the interface, and
which follow the general direction of the interface even when it changes direction sharply. A further characteristic
is the frequent development of only one of the possible Widmanstätten variants, for example VC plates in a
particular region are all only of one variant of the habit, i.e. that in which the plates are most nearly parallel to the
interface.

Appendix D. Page 75 of 116.


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The extremely fine scale of this phenomenon in vanadium steels, which also occurs in Ti and Nb steels, is due to
the rapid rate at which the γ/α transformation takes place. At the higher transformation temperatures, the slower
rate of reaction leads to coarser structures. Similarly, if the reaction is slowed down by addition of further alloying
elements, e.g. Ni and Mn, the precipitate dispersion coarsens.
The scale of the dispersion also varies from steel to steel, being coarsest in chromium, tungsten and
molybdenum steels where the reaction is relatively slow, and much finer in steels in which vanadium, niobium
and titanium are the dominant alloying elements and the transformation is rapid.
Transformation diagrams for alloy steels. The transformation of austenite below the eutectoid temperature can
best be presented in an isothermal transformation diagram, in which the beginning and end of transformation is
plotted as a function of temperature and time. Such curves are known as time-temperature-transformation, or
TTT curves, and form one of the important sources of quantitative information for the heat treatment of steels.
In the simple case of a eutectoid plain carbon steel, the curve is roughly C-shaped with the pearlite reaction
occurring down to the nose of the curve and a little beyond. At lower temperatures bainite and martensite are
formed. The diagrams become more complex for hypo- and hyper-eutectoid alloys as the ferrite or cementite
reactions have also to be represented by additional lines

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Alloying and Its Effects on the Critical Temperature, Hardness


and Tensile Strength

Alloying elements have significant effect on the iron-iron carbide equilibrium diagram. The addition of some of
these alloying elements will widen the temperature range through which austenite (gamma -iron) is stable while
other elements will constrict the temperature range. What this means is that some elements will raise and some
elements will lower the critical temperature of steel.

Manganese, cobalt, and nickel increase the temperature range through which austenite is stable. This also
means that the lower critical temperature of steel will be lowered by these alloying elements. Other alloying
elements that lower the critical temperature of steel are carbon, copper and zinc. The alloying elements that are
used to reduce the critical temperature are highly soluble in the gamma iron (austenite). Figure 1 shows the
effect of manganese on the critical temperature of steel.

Figure 1. The effect of alloying with manganese on the critical temperature of steel and austenite (γ-iron) phase
transformation zone on the iron-iron carbide diagram..

Alloys such as aluminum, chromium, molybdenum, phosphorus, silicon, tungsten tend to form solid solutions
with alpha iron (ferrite). This constricts the temperature region through which gamma iron (austenite) is stable.
As shown in Figure 2, chromium at different percentages constricts the critical temperature range which results
in a marked reduction of the region where austenite is stable.

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Figure 2. Effect of alloying with chromium on the critical temperature of steel and austenite (g -iron) phase
transformation zone on the iron-iron carbide diagram.

The elements shown in Figure 3 have the greatest solubility in ferrite and also influence the hardenability of iron
when in the presence of carbon. With a slight increase in the carbon content, they respond markedly to heat
treating, because carbon acts as a ferrite strengthener. As indicated in Figure 3, Phosphorus will improve the
hardness of the ferrite significantly by adding only a very small percentage of Phosphorus, while Chromium will
not strengthen the ferrite that well even at very high percentage of Chromium addition to the steel

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Figure 3. The effect of various alloying elements on the hardness of steel.

Figure 4 shows the effect of furnace cooling vs. air cooling on the tensile strength of steel for three different
percentages of carbon in the presence of chromium. As this figure indicates, furnace cooling has very little effect
on the tensile strength of the material. The addition of chromium does not change the tensile strength properties
when the steel is cooled in the furnace. If the same steels are air cooled at the same rate, the slope of the curves
increases significantly which means that a slight increase in the chromium content increases the strength
drastically when air cooling is applied.

Figure 4. Effect of different percentages of carbon on the tensile strength of steel in the presence of chromium.

Appendix D. Page 79 of 116.


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Control of High Strength Low Alloy (HSLA) Steel Properties

Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The exceptions
are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels with martensite
dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation of eutectoid
structures for strengthening, while the ferritic-pearlitic HSLA steels generally require strengthening of the ferrite.
Pearlite is generally an undesirable strengthening agent in structural steels because it reduces impact toughness
and requires higher carbon contents. Moreover, yield strength is largely unaffected by a higher pearlite content.
Strengthening Mechanisms in Ferrite
The ferrite in HSLA steels is typically strengthened by grain refinement, precipitation hardening, and, to a lesser
extent, solid-solution strengthening. Grain refinement is the most desirable strengthening mechanism because it
improves not only strength but also toughness.
Grain refinement is influenced by the complex effects of alloy design and processing methods. For example, the
various methods of grain refinement used in the three different stages of hot rolling (that is, reheating, hot rolling,
and cooling) include:
The addition of titanium or aluminum to retard austenite grain growth when the steel is reheated for hot
deformation or subsequent heat treatment
The controlled rolling of microalloyed steels to condition the austenite so that it transforms into fine-grain ferrite
The use of alloy additions and/or faster cooling rates to lower the austenite-to-ferrite transformation temperature.
The use of higher cooling rates for grain refinement may require consideration of its effect on precipitation
strengthening and the possibility of undesirable transformation products.
Precipitation strengthening occurs from the formation of finely dispersed carbonitrides developed during heating
and cooling. Because precipitation strengthening is generally associated with a reduction in toughness, grain
refinement is often used in conjunction with precipitation strengthening to improve toughness.
Precipitation strengthening is influenced by the type of carbonitride, its grain size, and, of course, the number of
carbonitrides precipitated. The formation of MC is the most effective metal carbide in the precipitation
strengthening of microalloyed niobium, vanadium, and/or titanium steels. The number of fine MC particles
formed during heating and cooling depends on the solubility of the carbides in austenite and on cooling rates.
Steelmaking
Precise steelmaking operations are also essential in controlling the properties and chemistry of HSLA steels.
Optimum property levels depend on such factors as the control of significant alloying elements and the reduction
of impurities and nonmetallic inclusions.
Developments in secondary steelmaking such as desulphurization, vacuum degassing, and argon shrouding
have enabled better control of steel chemistry and the effective use of microalloyed elements. Compositional
limits for HSLA steel grades described in ASTM specifications the use of vacuum degassing equipment allows
the production of interstitial-free (IF) steels. The IF steels exhibit excellent formability, high elongation, and good
deep draw/ability.
Compositions and Alloying Elements
Chemical compositions for the HSLA steels are specified by ASTM standards. The principal function of alloying
elements in these ferrite-pearlite HSLA steels, other than corrosion resistance, is strengthening of the ferrite by

Appendix D. Page 80 of 116.


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grain refinement, precipitation strengthening, and solid-solution strengthening. Solid-solution strengthening is


closely related to alloy contents, while grain refinement and precipitation strengthening depend on the complex
effects of alloy design and thermo-mechanical treatment.
Alloying elements are also selected to influence transformation temperatures so that the transformation of
austenite to ferrite and pearlite occurs at a lower temperature during air cooling. This lowering of the
transformation temperature produces a finer-grain transformation product, which is a major source of
strengthening. At the low carbon levels typical of HSLA steels, elements such as silicon, copper, nickel, and
phosphorus are particularly effective for producing fine pearlite. Element such as, manganese and chromium,
which are present in both the cementite and ferrite, also strengthen the ferrite by solid-solution strengthening in
proportion to the amount, dissolved in the ferrite.
In the presence of alloying elements, the practical maximum carbon content at which HSLA steels can be used in
the as-cooled condition is approximately 0.20%. Higher levels of carbon tend to form martensite or bainite in the
microstructure of as-rolled steels, although some of the higher-strength low-alloy steels have carbon contents
that approach 0.30%.
The required strength is developed by the combined effect of:
Fine grain size developed during controlled hot roiling and enhanced by microalloyed elements (especially
niobium)
Precipitation strengthening caused by the presence of vanadium, niobium, and titanium in the composition.
Nitrogen additions to high-strength steels containing vanadium are limited to 0.005% and have become
commercially important because such additions enhance precipitation hardening. The precipitation of vanadium
nitride in vanadium-nitrogen steels also improves grain refinement because it has a lower solubility in austenite
than vanadium carbide.
Manganese is the principal strengthening element in plain carbon high-strength structural steels. It functions
mainly as a mild solid-solution strengthener in ferrite, but it also provides a marked decrease in the
austenite-to-ferrite transformation temperature. In addition, manganese can enhance the precipitation
strengthening of vanadium steels and. to a lesser extent, niobium steels.
One of the most important applications of silicon is its use as a deoxidizer in molten steel. Silicon has a
strengthening effect in low-alloy structural steels. In larger amounts, it increases resistance to scaling at elevated
temperatures. Silicon has a significant effect on yield strength enhancement by solid-solution strengthening and
is widely used in HSLA steels for riveted or bolted structures.
Copper in levels in excess of 0.50% also increases the strength of both low- and medium-carbon steels by virtue
of ferrite strengthening, which is accompanied by only slight decreases in ductility. Copper can be retained in
solid solution even at the slow rate of cooling obtained when large sections are normalized, but it is precipitated
out when the steel is reheated to about 510 to 605°C (950 to 1125°F). At about 1% copper, the yield strength is
increased by about 70 to 140 MPa regardless of the effects of other alloying elements. Copper in amounts up to
0.75% is considered to have only minor adverse effects on notch toughness or weldability. Copper precipitation
hardening gives the steel the ability to be formed extensively and then precipitation hardened as a complex
shape or welded assembly.
The atmospheric-corrosion resistance of steel is increased appreciably by the addition of phosphorus, and when
small amounts of copper are present in the steel, the effect of the phosphorus is greatly enhanced. When both
phosphorus and copper are present, there is a greater beneficial effect on corrosion resistance than the sum of
the effects of the individual elements.
Chromium is often, added with copper to obtain improved atmospheric-corrosion resistance.

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Nickel is often added to copper-bearing steels to minimize hot shortness.


Molybdenum in hot-rolled HSLA steels is used primarily to improve hardenability when transformation products
other than ferrite-pearlite are desired. Molybdenum (0.15 to 0.30%) in microalloyed steels also increases the
solubility of niobium in austenite, thereby enhancing the precipitation of NbC(N) in the ferrite. This increases the
precipitation-strengthening effect of NbC(N).
Aluminum is widely used as a deoxidizer and was the first element used to control austenite grain growth during
reheating. During controlled rolling, niobium and titanium are more effective grain refiners than aluminum.
Vanadium strengthens HSLA steels by both precipitation hardening the ferrite and refining the ferrite grain size.
The precipitation of vanadium carbonitride in ferrite can develop a significant increase in strength that depends
not only on the rolling process used, but also on the base composition. Carbon contents above 0.13 to 0.15%
and manganese content of 1% or more enhances the precipitation hardening, particularly when the nitrogen
content is at least 0.01%.
Titanium is unique among common alloying elements in that it provides both precipitation strengthening and
sulfide shape control. Small amounts of titanium (<0.025%) are also useful in limiting austenite grain growth.
However, it is useful only in fully killed (aluminum deoxidized) steels because of its strong deoxidizing effects, the
versatility of titanium is limited because variations in oxygen, nitrogen, and sulfur affect the contribution of
titanium as carbide strengthened.
Zirconium can also be added to killed high-strength low-alloy steels to improve inclusion characteristics,
particularly in the case of sulfide inclusions, for which changes in inclusion shape improve ductility in transverse
bending.
Boron has no effect on the strength of normal hot-rolled steel but can considerably improve hardenability when
transformation products such as acicular ferrite are desired in low-carbon hot-rolled plate.
Treatment with calcium is preferred for sulfide inclusion shape control.
Controlled Rolling
The hot-rolling process has gradually become a much more closely controlled operation, and controlled rolling is
now being increasingly applied to microalloyed steels with compositions carefully chosen to provide optimum
mechanical properties at room temperature.
Controlled rolling is a procedure whereby the various stages of rolling are temperature controlled, with the
amount of reduction in each pass predetermined and the finishing temperature precisely defined. This
processing is widely used to obtain reliable mechanical properties in steels for pipelines, bridges, offshore
platforms, and many other engineering applications. The use of controlled rolling has resulted in improved
combinations of strength and toughness and further reductions in the carbon content of microalloyed HSLA
steels

Appendix D. Page 82 of 116.


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Influence of Alloying Elements on Steel Microstructure

It is a long-standing tradition to discuss the various alloying elements in terms of the properties they confer on
steel. For example, the rule was that Chromium (Cr) makes steel hard whereas Nickel (Ni) and Manganese (Mn)
make it tough. In saying this, one had certain types of steel in mind and transferred the properties of particular
steel to the alloying element that was thought to have the greatest influence on the steel under consideration.
This method of reasoning can give false impressions and the following examples will illustrate this point.

When we say that Cr makes steel hard and wear-resisting we probably associate this with the 2% C, 12% Cr tool
steel grade, which on hardening does in fact become very hard and hard-wearing. But if, on the other hand, we
choose a steel containing 0.10% C and 12% Cr, the hardness obtained on hardening is very modest.
It is quite true that Mn increases steel toughness if we have in mind the 13% manganese steel, so-called
Hadfield steel. In concentrations between l% and 5%, however, Mn can produce a variable effect on the
properties of the steel it is alloyed with. The toughness may either increase or decrease.
A property of great importance is the ability of alloying elements to promote the formation of a certain phase or to
stabilize it. These elements are grouped as austenite-forming, ferrite-forming, carbide-forming and
nitride-forming elements.

Austenite-forming elements
The elements C, Ni and Mn are the most important ones in this group. Sufficiently large amounts of Ni or Mn
render a steel austenitic even at room temperature. An example of this is the so-called Hadfield steel which
contains 13% Mn, 1,2% Cr and l% C. In this steel both the Mn and C take part in stabilizing the austenite.
Another example is austenitic stainless steel containing 18% Cr and 8% Ni.
The equilibrium diagram for iron-nickel, Figure 1, shows how the range of stability of austenite increases with
increasing Ni-content.

Appendix D. Page 83 of 116.


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Figure 1. Fe-Ni equilibrium diagram


More diagrams: http://www.calphad.com/phase_diagrams.html

An alloy containing 10% Ni becomes wholly austenitic if heated to 700°C. On cooling, transformation from g to a
takes place in the temperature range 700-300°C.
Ferrite-forming elements
The most important elements in this group are Cr, Si, Mo, W and Al. The range of stability of ferrite in
iron-chromium alloys is shown in Figure 2. Fe-Cr alloys in the solid state containing more than 13% Cr are ferritic
at all temperatures up to incipient melting. Another instance of ferritic steel is one that is used as transformer
sheet material. This is a low-carbon steel containing about 3% Si.

Appendix D. Page 84 of 116.


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Figure 2. Cr-Fe equilibrium diagram

Multi-alloyed steels
The great majority of steels contain at least three components. The constitution of such steels can be deduced
from ternary phase diagrams (3 components). The interpretation of these diagrams is relatively difficult and they
are of limited value to people dealing with practical heat treatment since they represent equilibrium conditions
only. Furthermore, since most alloys contain more than three components it is necessary to look for other ways
of assessing the effect produced by the alloying elements on the structural transformations occurring during heat
treatment.
One approach that is quite good is the use of Schaeffler diagrams (see Figure 3). Here the austenite formers are
set out along the ordinate and the ferrite formers along the abscissa. The original diagram contained only Ni and
Cr but the modified diagram includes other elements and gives them coefficients that reduce them to the
equivalents of Ni or Cr respectively. The diagram holds good for the rates of cooling which result from welding.

Appendix D. Page 85 of 116.


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Figure 3. Modified Schaeffler diagram

Appendix D. Page 86 of 116.


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A 12% Cr steel containing 0.3% C is martensitic, the 0.3% C gives the steel a nickel equivalent of 9. An 18/8 steel
(18% Cr, 8% Ni) is austenitic if it contains 0-0.5% C and 2% Mn. The Ni content of such steels is usually kept
between 9% and 10%.
Hadfield steel with 13% Mn (mentioned above) is austenitic due to its high carbon content. Should this be
reduced to about 0.20% the steel becomes martensitic.
Carbide-forming elements
Several ferrite formers also function as carbide formers. The majority of carbide formers are also ferrite formers
with respect to Fe. The affinity of the elements in the line below for carbon increases from left to right.
Cr, W, Mo, V, Ti, Nb, Ta, Zr.
Some carbides may be referred to as special carbides, i.e. non-iron-containing carbides, such as Cr7C3 W2C,
VC, Mo2C. Double or complex carbides contain both Fe and a carbide-forming element, for example Fe4W2C.
High-speed and hot-work tool steels normally contain three types of carbides, which are usually designated M6C,
M23C6 and MC. The letter M represents collectively all the metal atoms. Thus M6C represents Fe4W2C or
Fe4Mo2C; M23C6 represents Cr23C6 and MC represents VC or V4C3.
Carbide stabilizers
The stability of the carbides is dependent on the presence of other elements in the steel. How stable the carbides
are depends on how the element is partitioned between the cementite and the matrix. The ratio of the
percentage, by weight, of the element contained in each of the two phases is called the partition coefficient K.
The following values are given for K:

Al Cu P Si Co Ni W Mo Mn Cr Ti Nb Ta
0 0 0 0 0.2 0.3 2 8 11,4 28 Increasing

Note that Mn, which by itself is a very weak carbide former, is a relatively potent carbide stabilizer. In practice, Cr
is the alloying element most commonly used as a carbide stabilizer.
Malleable cast iron (i.e. white cast iron that is rendered soft by a graphitizing heat treatment called malleablizing)
must not contain any Cr. Steel containing only Si or Ni is susceptible to graphitization, but this is most simply
prevented by alloying with Cr.
Nitride-forming elements
All carbide formers are also nitride formers. Nitrogen may be introduced into the surface of the steel by nitriding.
By measuring the hardness of various nitrided alloy steels it is possible to investigate the tendency of the
different alloying elements to form hard nitrides or to increase the hardness of the steel by a mechanism known
as precipitation hardening.
The results obtained by such investigations are shown in Figure 4, from which it can be seen that very high
hardnesses result from alloying a steel with Al or Ti in amounts of about 1,5%.

Appendix D. Page 87 of 116.


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Figure 4. Effect of alloying element additions on hardness after nitriding Base composition: 0.25% C, 0.30% Si,
0.70% Mn

On nitriding the base material in Figure 4, hardness of about 400 HV is obtained and according to the diagram
the hardness is unchanged if the steel is alloyed with Ni since this element is not a nitride former and hence does
not contribute to any hardness increase

Appendix D. Page 88 of 116.


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Martensite in Austenitic Stainless Steel Welds

Background

Martensite is a crystal structure that forms in steels during rapid cooling. Cooling rates are dependent on the
particular chemistry of the steel. Certain conditions can be met that will cause martensite formation in austenitic
stainless steels.

Long, needle-like clusters of crystals in the metal characterize martensite. The martensite crystals have a highly
stressed body centered tetragonal structure. In austenitic stainless steels and the austenite phase of a magnetic
(austenitic/ferritic) stainless, when martensite is present in a weld, don't expect it to pass the bend test. The weld
will not have the toughness and ductility that we normally expect from a stainless steel, and in some
circumstances there may be unanticipated corrosion.

Fillet Composition

With only one exception, adding alloying elements to steel allows martensite to form at a slower cooling rate.
That exception is cobalt, which works the other way. With cobalt, martensite will form at a faster cooling rate.

We recognize that the actual composition of the weld fillet will vary along a line running across or bisecting the
weld fillet. On the centerline, we expect the fillet composition to be closer to the wire composition. Approaching
each base metal, the composition shifts from the filler metal composition towards each base metal. In welding
metallurgy, we mark on the phase diagram the chemistry of one base metal and the chemistry of the filler wire.
We find that the actual fillet compositions lie on the line drawn on the phase diagram. When the base metals are
different, it takes different lines on the phase diagram to represent the compositions approaching each base
metal.

Predicting Martensite

The results and microstructural consequences of this sort of exercise in physical metallurgy appeared in 1949 as
the "Schaeffler Diagram". Our technology did not stand still and the Diagram iterated through several updates.
The 1994 Winter Addendum to the ASME Code brought us the Welding Research Council's "WRC-1992
Diagram" which continues to be extensively used. Still, there has been a problem associated with manganese,
which brought yet another modification into use. The analysis behind the modification appears, for example, in
D.J. Kotecki's, "A martensite boundary on the WRC-1992 diagram" (Welding Journal , Vol. 78, No. 5, pp
180-192).

In lots of cases the 1% manganese line satisfactorily predicts martensite or not martensite. However, we
sometimes encounter steels having higher manganese and quite often encounter much lower. High side

Appendix D. Page 89 of 116.


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examples include 1.0-1.5% manganese in a 309L filler wire, 4% in a 307, and 6% in the European 18 8 Mn filler
wire. On the low side, if you are joining stainless to a modern carbon steel, the manganese can be quite low,
perhaps even 0.3%.

(The 1949 Schaeffler diagram - click image to enlarge)

To enter the modified Diagram, we need to calculate two numbers roughly based on chromium and nickel
content. We also have to apply a lot of welding "know-how" as to the mixing of the metals.

Calculate the

Nickel Ni Equivalent = %Ni + 35%C + 20%Mn + 0.25%Cu


Chrome Cr Equivalent = %Cr + Mo + 1.5%Si + 0.7%Nb

The Amount of Nitrogen

One of the problems we have to also confront is the amount of nitrogen. The best shielding practice with a wire
electrode might not introduce nitrogen. Flux cored electrodes tend to add nitrogen. For example, the metal in a
flux cored electrode might analyze to 0.05% nitrogen while it deposits as 0.075% nitrogen. Most of us deal with
the nitrogen by first plotting the points with only the known nitrogen and then we plot the nearby point based on

Appendix D. Page 90 of 116.


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our estimate of the actual nitrogen. The compositions at risk are those on the Diagram and below the indicated
manganese brands. Within the bands the diagram is known to be imprecise.

In practice, you have to cope with the range of compositions between one base metal and the filler metal, and
between the other base metal and the filler metal. You could put all of your predicted nickel and chromium
equivalent compositions on the graph. However, examining the diagram we see that the compositions more at
risk for forming martensite are those with low nickel and chromium equivalent numbers, coupled with low
manganese. After a little practice with the diagram we know pretty well which compositions are likely to be at risk
and we tend to plot only those numbers.

A warning: Notice that all of the alloying elements in the calculation contribute to hardenability. Should either
base metal or the filler metal contain any unlisted elements which are known to contribute to hardenability then
the Diagram doesn't apply. After decades of absence, tungsten is showing up mostly as a substitute for
molybdenum and mostly in Russian and Chinese metals. In doing the calculation the practice is to lump the
tungsten with the moly on a 1:1 basis. When forced to do it, welding metallurgists may tweak the calculations a
little to reflect other unlisted elements, however, there isn't much of a research foundation on which to base such
adjustments.

Ferrite Number

The 300 series of stainless steels is austenitic (non-magnetic) while the duplex stainless steels are mixed
austenite and ferrite. In the field, the amount of ferrite is measured through its magnetic response. The portable
meter is calibrated for % ferrite and it is called the "ferrite number". Martensite gives a magnetic response, but
not as strongly as ferrite, so when it is present it contributes to the "ferrite number".

Recognize also that perfectly good austenitic stainless steel that has been heavily cold worked can become
slightly magnetic and give a ferrite number even though ferrite nor martensite are present.

In the upper right side of the diagram there is a cluster of lines of constant ferrite number. The upper left line is
1% ferrite number which is nominally 99% austenite and 1% ferrite. The last line along the lower right side of the
cluster is nominally 98% ferrite and 2% austenite.

Learning by Doing (and "cya")

Good record keeping means photocopying a bunch of diagrams and every time you confront the martensite
issue you make a record of how you calculated the nickel and chromium equivalents. You plot these on the
graph, draw the lines between and estimate an adjustment for nitrogen. You note the ferrite number and whether
the bend test is pass or fail.

You don't just do the exercise for samples that fail the bend test. Otherwise you won't learn the limits for welds
that pass every time! If testing the weld for its ferrite number is worthwhile then making the record is also
worthwhile. The day will come when you note the manganese is low and you make yourself into a hero when you
predict the need for a little preheat.

Appendix D. Page 91 of 116.


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(The WRC-1992 Diagram modified to reflect experience with manganese. Martensite is predicted to form with
composition equivalents below and to the left of the manganese bands. Reprinted from Advanced
Materials&Process, June 1000, p. 75 - click image to enlarge)

There will be discrepancies. When it happens it most likely means that you misjudged the effect of cooling rate,
or you didn't get the chemistry right, or the basic diagram is imperfect!

Appendix D. Page 92 of 116.


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Effects on the martensite, pearlite and bainite formation

Effect on the temperature of martensite formation

All alloying elements with the possible exception of Co, lower Ms the temperature of the start of the martensite
formation, as well as Mf, the finish of the martensite formation, i.e. at 100% martensite. For the majority of steels
containing more than 0.50% C, Mf lies below room temperature.

This implies that after hardening these steels practically always contain some residual austenite. Ms may be
calculated from the equation given below, by inserting the percentage concentration of each alloying element in
the appropriate term. The equation is valid only if all the alloying elements are completely dissolved in the
austenite.

Ms = 561 - 474C - 33Mn - 17Ni - 17Cr - 21Mo

For high-alloy and medium-alloy steels Stuhlmann has suggested the following equation:

Ms(°C) = 550 - 350C - 40Mn - 20Cr - 10Mo - 17Ni - 8W - 35V - 10Cu + 15Co + 30Al

It can be noted that carbon has the strongest influence on the Ms temperature. Figures 1 and 2 show diagrams
with an example of experimental results of the effect of Mn and Ni on the Ms temperature of various types of
steel.

Figure 1. Effect of Mn on the Ms - temperature (after Russel and McGuire,


Payson and Savage, Zyuzin, Grange and Stewart)

Appendix D. Page 93 of 116.


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Figure 2. Effect of Ni on the Ms - temperature (after Russel and McGuire,


Payson and Savage, Zyuzin, Grange and Stewart)

Effect on the formation of pearlite and bainite during the isothermal transformation

All alloying elements except Co delay the formation of ferrite and cementite. It is very difficult to formulate any
general rules regarding the influence exerted by the various alloying elements. However, it has definitely been
found that some elements affect the bainite transformation more than the pearlite transformation, while other
elements act in the opposite manner.

Certain elements will, paradoxically, accelerate the transformations if their concentration increases beyond a
certain limiting value, this limit been affected by other alloying elements present. For case-hardening and tool
steels the time taken to initiate the pearlite-bainite transformation is reduced as the carbon content exceeds
about 1%. For tool steels and constructional steels Si-concentrations of 1,5% and above have been found to
promote pearlite formation.

As a general principle it may be stated that by increasing the concentration of one alloying element by some few
percent and the basic carbon content being kept about 0.50%, only a relatively small retardation of the
transformation rates is noticed. For plain carbon steels a successive increase in C from 0.30% to 1% produces
but a negligible effect. It is only in conjunction with several alloying elements that a more noticeable effect is
produced.

The diagram in Figure 3, applicable to steel W 1 (l% C) will serve as a basis for this discussion. The shortest
transformation time for this steel is less than 1/8th second. Note that the time scale is logarithmic; hence there is
no zero time. As has been mentioned previously, both pearlite and bainite form simultaneously in this steel at
about 550°C. Since the curves overlap it is customary to draw only one curve. With increasing contents of certain
alloying elements, however, the noses of the pearlite and bainite curves will separate.

The structures shown in Figure 3 are obtained by austenitizing samples of steel W 1 at 780°C for 10 min and
quenching in a salt bath at various temperatures. After holding them for predetermined times at various
temperatures they are finally quenched in water. Before the salt-bath quenching the steel contains undissolved

Appendix D. Page 94 of 116.


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carbides but in view of the composition of the austenite the steel may be regarded as an eutectoid one. The
diagram should be studied with the aid of the explanatory text below.

Figure 3. TTT diagram for isothermal transformation of steel W 1 (1% C)


A = austenite, B = bainite,
Ms = start of martensite transformation,
M50 = 50% M, P = pearlite

1. Quenching in a liquid bath at 700°C; holding time 4 min. During this interval the C has
separated out, partly as pearlite lamellae and partly as spheroidized cementite. Hardness
225 HV.
2. Quenching to 575°C, holding time 4 s. A very fine, closely spaced pearlite as well as some
bainite has formed. Note that the amount of spheroidized cementite is much less than in the
preceding case. Hardness 380 HV.
3. Quenching to 450°C, holding time 60 s. The structure consists mainly of bainite. Hardness
410 HV.
4. Quenching to 20°C (room temperature). The matrix consists of, roughly, 93% martensite
and 7% retained austenite. There is some 5% cementite as well which has not been included
in the matrix figure. Hardness 850 HV.

Appendix D. Page 95 of 116.


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Steel Alloys

Below is a list of some SAE-AISI designations for Steel (the xx in the last two digits indicate the carbon
content in hundredths of a percent)

Carbon Steels
10xx Plain Carbon
11xx Resulfurized
12xx Resulfurized and rephosphorized
Manganese steels
13xx Mn 1.75
Nickel steels
23xx Ni 3.5
25xx Ni 5.0
Nickel Chromium Steels
31xx Ni 1.25 Cr 0.65-0.80
32xx Ni 1.75 Cr 1.07
33xx Ni 3.50 Cr 1.50-1.57
34xx Ni 3.00 Cr 0.77
Chromium Molybdenum
steels
41xx Cr 0.50-0.95 Mo 0.12-0.30
Nickel Chromium
Molybdenum steels
43xx Ni 1.82 Cr 0.50-0.80 Mo 0.25
47xx Ni 1.05 Cr 0.45 Mo 0.20 – 0.35
86xx Ni 0.55 Cr 0.50 Mo 0.20
Nickel Molybdenum
steels
46xx Ni 0.85-1.82 Mo 0.20
48xx Ni 3.50 Mo 0.25
Chromium steels
50xx Cr 0.27- 0.65 Illustration of effect of Carbon content on
51xx Cr 0.80 – 1.05 Steel Hardness

Appendix D. Page 96 of 116.


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Carbon Steel to Austenitic Steel

When a weld is made using a filler wire or consumable, there is a mixture in the weld consisting of approximately
20% parent metal and 80% filler metal alloy ( percentage depends on welding process, type of joint and welding
parameters).
Any reduction in alloy content of 304 / 316 type austenitic is likely to cause the formation of martensite on
cooling. This could lead to cracking problems and poor ductility. To avoid this problem an over alloyed filler
metal is used, such as a 309, which should still form austenite on cooling providing dilution is not excessive.
The Shaeffler diagram can be used to determine the type of microstructure that can be expected when a filler
metal and parent metal of differing compositions are mixed together in a weld.
The Shaeffler Diagram

The Nickel and other elements that form Austenite, are plotted against Chrome and other elements that form
ferrite, using the following formula:-
Nickel Equivalent = %Ni + 30%C + 0.5%Mn
Chrome Equivalent = %Cr + Mo + 1.5%Si + 0.5%Nb
Example, a typical 304L = 18.2%Cr, 10.1%Ni, 1.2%Mn, 0.4%Si, 0.02%C
Ni Equiv = 10.1 + 30 x 0.02 + 0.5 x 1.2 = 11.3
Cr Equiv = 18.2 + 0 + 1.5 x 0.4 + 0 = 18.8

Appendix D. Page 97 of 116.


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A typical 309L welding consumable Ni Equiv = 14.35, Cr Equiv = 24.9


The main disadvantage with this diagram is that it does not represent Nitrogen, which is a very strong Austenite
former.
Ferrite Number
The ferrite number uses magnetic attraction as a means of measuring the proportion of delta ferrite
present. The ferrite number is plotted on a modified Shaeffler diagram, the Delong Diagram. The Chrome and
Nickel equivalent is the same as that used for the Shaeffler diagram, except that the Nickel equivalent includes
the addition of 30 times the Nitrogen content.

Examples

Appendix D. Page 98 of 116.


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The Shaeffler diagram above illustrates a carbon steel C.S , welded with 304L filler. Point A represents the
anticipated composition of the weld metal, if it consists of a mixture of filler metal and 25% parent metal. This
diluted weld, according to the diagram, will contain martensite. This problem can be overcome if a higher
alloyed filler is used, such as a 309L, which has a higher nickel and chrome equivalent that will tend to pull point
A into the austenite region.
If the welds molten pool spans two different metals the process becomes more complicated. First plot both
parent metals on the shaeffler diagram and connect them with a line. If both parent metals are diluted by the
same amount, plot a false point B on the diagram midway between them. (Point B represents the microstructure
of the weld if no filler metal was applied.)

Next, plot the consumable on the diagram, which for this example is a 309L. Draw a line from this point to false
point B and mark a point A along its length equivalent to the total weld dilution. This point will give the
approximate microstructure of the weld metal. The diagram below illustrates 25% total weld dilution at point A,
which predicts a good microstructure of Austenite with a little ferrite.

Appendix D. Page 99 of 116.


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The presence of martensite can be detected by subjecting a macro section to a hardness survey, high hardness
levels indicate martensite. Alternatively the weld can be subjected to a bend test ( a side bend is required by the
ASME code for corrosion resistant overlays), any martensite present will tend to cause the test piece to break
rather than bend.
However the presence of martensite is unlikely to cause hydrogen cracking, as any hydrogen evolved during the
welding process will be absorbed by the austenitic filler metal.

More reading:
http://nhml.com/search.cfm?zoom_query=stainless+steel&zoom_per_page=10&zoom_and=0&zoom_sort=0

Appendix D. Page 100 of 116.


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Appendix D. Page 101 of 116.


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Selection of Age-Hardenable Superalloys

By Richard B. Frank
High-Temperature R&D
Carpenter Technology Corp., Reading, PA, USA

Superalloys are high-performance materials designed to provide high mechanical strength and resistance to
surface degradation at high temperatures of 1200°F (650°C) or above. They combine high tensile, creep-rupture,
and fatigue strength; good ductility and toughness, with excellent resistance to oxidation and hot corrosion.
Furthermore, superalloys are designed to retain these properties during long-term exposures at the elevated
temperatures.

This article focuses on the wrought age-hardenable alloys, which are the most commonly used superalloys.
Wrought materials can be formed using hot and cold working operations. Not discussed here are the cast,
powder (P/M), and oxide dispersion strengthened (ODS) superalloys that can also offer enhanced properties.

The first age-hardenable, high-temperature alloy dates back to about 1929 when various developers added
titanium and aluminum to the standard 80% nickel/20% chromium resistance wire alloy. This was a precursor to
the 80A nickel-base superalloy, developed in 1940-1944, but still in use today.

Little was done to advance the original age-hardenable alloys until the time period of 1935-1944 when World
War II spurred demand for improved alloys that could be used in the early aircraft gas turbine engines. Alloy
development activity exploded in the 1950’s and 1960’s to keep pace with the demands of the gas turbine engine
industry. Progress in superalloy development not only made the jet engine possible, but allowed for constantly
increasing thrust-to-weight ratios over the last 60 years.

Applications

The primary application for superalloys is still in hot sections of aircraft gas turbine engines, accounting for over
50% of the weight of advanced engines. However, the excellent performance of these materials at elevated
temperatures has expanded their application far beyond one industry.

In addition to the aerospace industry, these alloys are used in turbine engines for marine, industrial, land-based
power generation, and vehicular applications. Specific engine parts using superalloys include turbine discs,
blades, compressor wheels, shafts, combustor cans, afterburner parts and engine bolts.

Beyond the gas turbine engine industries, superalloys are commonly used for applications in rocket engines,
space, petrochemical/energy production, internal combustion engines, metal forming (hot-working tools and
dies), heat-treating equipment, nuclear power reactors, and coal conversion.

Appendix D. Page 102 of 116.


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While these alloys are primarily used for service at elevated temperatures above 1000°F (540°C), the
characteristics of high strength and excellent environmental resistance have made some superalloys an
excellent choice for lower-temperature applications. Examples are prosthetic devices in the medical industry and
components for deep sour gas wells in the oil/gas exploration industry.

Chemical Composition

Table 1 contains the nominal compositions of the most common wrought age-hardenable superalloys. These
alloys contain various combinations of nickel, iron, cobalt, and chromium with lesser amounts of other elements
including molybdenum, niobium, titanium, and aluminum. With minor additions of beneficial elements such as
boron and zirconium, these alloys may contain up to 12 intentional additions. All these additions help to impart
and maintain the desired properties at elevated temperatures.

Many other elements such as silicon, phosphorus, sulfur, oxygen, nitrogen and a larger number of tramp
elements (like lead, bismuth, selenium) must be tightly controlled in superalloys to avoid detrimental effects on
high-temperature properties. These minor and tramp elements are controlled during raw material selection prior
to melting, as well as during the melting/remelting processes.

Appendix D. Page 103 of 116.


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Superalloys can be classified into nickel-base, iron-base, and cobalt-based groups. Nickel-based superalloys
(>50% Ni) are the most common group. About half of the alloys in Table 1 are considered nickel-base alloys and
the others contain large additions of nickel. The nickel base has a high tolerance for alloy additions that might
otherwise cause phase instability leading to loss of strength, ductility, and/or environmental resistance.

Iron-based superalloys are less costly, but are less tolerant of alloying additions and typically have lower
mechanical properties and maximum temperature limitations. Examples are Pyromet® Alloy A-286 and NCF
3015 (Ni-30) alloy. These alloys contain an austenitic stainless steel base with additions of nickel, titanium, and
aluminum to promote age hardening. Pyromet Alloy 706 and Pyromet Alloy 901 have similar amounts of nickel
and iron and can be considered nickel-iron-base superalloys. The higher nickel levels of 901 and 706 alloys
allow for larger additions of strengthening elements without undesirable effects.

Although there are some cobalt-base superalloys, they are significantly higher in cost and typically cannot be
age hardened to high strength levels. However, cobalt is an important alloying addition to nickel-based alloys
because it extends the maximum temperature for usage by reducing the solubility of the age-hardening phase.
Waspaloy and Pyromet Alloy 41 and Pyromet Alloy 720 are nickel-base alloys with 10-15% cobalt additions.
These alloys have the highest temperature capability of the common wrought age-hardenable superalloys.

Chromium, usually in the range of 14 to 23 weight percent, is a critical alloying addition to nearly all superalloys.
As in stainless steels, chromium forms a tightly-adherent, protective oxide film (Cr2O3) on the alloy surface to
resist oxidation and corrosion at high temperatures as well as corrosion at lower temperatures. This surface layer
protects the alloy from the harmful effects of the elements oxygen, nitrogen, and sulfur.

Although most superalloys contain at least 14% chromium, in some applications, it is critical to minimize thermal
expansion. Pyromet CTX-909 and Thermo-Span® alloys are considered low-expansion superalloys that have
low chromium contents to minimize expansion of the nickel-cobalt-iron base. Resistance to oxidation and hot
corrosion are reduced so high-temperature coatings are often applied prior to service. Of the two alloys, 909
alloy provides the lowest expansion coefficient while Thermo-Span alloy (5.5% chromium) provides improved
environmental resistance.

Refractory elements like molybdenum, tungsten, and niobium, with their large atomic diameters, increase high
temperature strength and stiffness by straining the nickel/iron base matrix. Alloys 901 and 41 contain larger
additions of molybdenum to increase this solid solution strengthening effect. Other alloying additions such as
chromium and aluminum also contribute to solid solution strengthening but to a lesser extent.

The elements titanium, aluminum, and niobium are added to the nickel or nickel-iron matrix to form an
intermetallic Ni3 (Al, Ti, Nb) phase during age-hardening heat treatments. The resultant gamma prime or gamma
double prime phases are the primary strengthening agents in superalloys. This will be discussed in more detail in
the next section on age-hardening.

Although elements such as boron, zirconium, and magnesium may be added at levels less than 0.1 weight
percent, the beneficial effects can be very potent. These elements segregate to and stabilize grain boundaries,
which significantly improves hot workability, high temperature strength and ductility. Small additions of carbon

Appendix D. Page 104 of 116.


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also may be added to form carbides that restrict grain growth and grain boundary sliding during high temperature
exposure.

Age-Hardening

The major strengthening method in superalloys is age-hardening. Yield strength of nickel alloys is typically
increased by a factor of two or three by precipitation of the gamma prime and/or gamma double prime, Ni3 (Al, Ti,
Nb) hardening phase. Although the phase is based on the nickel aluminide (Ni3Al) intermetallic, up to 60% of the
aluminum can be replaced by titanium or niobium, which actually increases strength of the alloy.

The gamma prime phase is rather unique in that its strength actually increases with temperature up to 1200°F
(650°C) and it is relatively ductile and resistant to oxidation. Gamma prime precipitates as very fine spheroidal or
cuboidal particles in the nickel-iron matrix during aging.

While most of the superalloys employ the titanium-rich gamma prime phase for age hardening, a niobium-rich
variant called gamma double prime is the primary strengthening phase in some superalloys such as Pyromet
Alloy 706 and Pyromet Alloy 718. The niobium-rich phase provides higher strength up to 1200°F (650°C) but is
unstable above 1200°F. Thus, 706 and 718 alloys have a lower temperature limit than the alloys strengthened
with the titanium-rich gamma prime phase. Since the gamma double prime reaction is more sluggish, these
alloys also tend to have better hot workability and weldability.

Heat Treatment

Proper heat treatment is critical to achieving the desired level of properties in age-hardenable superalloys.
Typical heat treatments for these alloys are listed in the mechanical property Tables 2 and 3. The initial solution
heat treatment typically dissolves all precipitated phases except for some primary carbide and nitride phases.
The typical range for the wrought age-hardenable superalloys is 1650-2100°F (900-1150°C) for 1 to 4 hours
followed by a rapid air cool or a quench in water, polymer or oil.

Appendix D. Page 105 of 116.


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Appendix D. Page 106 of 116.


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The selection of solution treatment time and temperature varies with the alloy and its phase solvus temperatures,
and also depends on the specific properties that are most important for the intended application. Alloys with
higher hardener contents (Ti, Al, Nb) require higher temperatures to solution any hardener phase that may have
precipitated during hot working or cooling. Best tensile and fatigue properties are typically obtained with lower
solution temperatures that result in a finer grain size. In contrast, better long-term stress-rupture and creep
properties are generally obtained with higher-temperature solution treatments that result in coarser grain size
and lower tensile yield strength. For these reasons, it is common to specify two or more preferred heat
treatments for superalloys.

In some cases, another objective of the solution treatment is to form a desirable distribution of a second phase
such as carbide in Pyromet 41 alloy and delta phase (Ni3Nb) in Pyromet 718 alloy. After solution treatment, one
or more aging treatments are applied to precipitate the hardening phase and possibly other phases in the

Appendix D. Page 107 of 116.


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desired amount and distribution. As with solution treatment, the selection of aging temperatures is dependent on
the alloy and the combination of properties desired.

The aging range for age-hardenable superalloys is 1150-1600°F (620-870°C). Aging times range from 4 hours to
24 hours. Double-aging treatments are quite common to maximize strength and to develop the best combination
of short-term tensile and long-term creep-rupture properties. The primary aging treatment precipitates a coarser
distribution of the hardener phase and may also improve the type and distribution of carbides on grain
boundaries.

The secondary age is typically about 200°F below the primary aging temperature, precipitating a finer dispersion
of the gamma prime phase. For some higher-strength applications, the alloy is direct aged after hot, warm, or
cold working without an intermediate solution treatment. The strain from working is used to further enhance
tensile and fatigue properties with some sacrifice in creep-rupture properties.

Mechanical Properties

For the design engineer or materials specifier, a review of terms defining applicable mechanical properties may
be helpful:

Tensile Properties – The design of load-bearing structures is often based on yield strength or, in some cases,
the ultimate tensile strength of the material. Yield strength is a measure of the maximum stress a material can
withstand before it permanently deforms. Tensile strength is a measure of the maximum stress a material can
withstand before it fractures. Elevated temperature tensile properties are most applicable to short-time
exposures at higher temperatures. Creep and stress-rupture properties are more applicable for longer
exposures.

Creep and Rupture Properties – Creep and rupture strengths become important when the material must
withstand the combined effects of high temperature and stress for long periods of time. At elevated temperatures,
metals will stretch or "creep" at stresses well below the yield strength. Superalloys are more resistant to creep
than low-alloy or stainless steels, but creep will still occur above about 1000°F (540°C). Creep properties are a
measure of the alloy’s resistance to stretching under a constant load. Stress-rupture or creep-rupture properties
are a measure of resistance to fracture under a constant load (creep test taken to fracture). Both properties are
expressed as stress or strength values that will cause a given amount of creep (0.1%-1%) or rupture in a given
amount of time (100 to 100,000 hours).

Tables 2 and 3 list typical tensile (yield) and stress-rupture strength properties of the age-hardenable superalloys
at temperatures of 1200-1600°F (650-870°C). Yield strengths at room temperature are also listed in Table 2.
These properties are shown graphically in Figures 1 and 2. It should be noted that the data represents
approximate nominal strength values for specific heat treatments. Actual values can vary by up to 35% due to
differences in composition, hot/cold working practices, and heat treatment.

Appendix D. Page 108 of 116.


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Appendix D. Page 109 of 116.


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For example, superalloys like Pyromet 718 and Waspaloy may contain several different aim compositions within
the broader industry ranges to optimize properties for specific applications. Higher levels of the age-hardening
elements titanium, aluminum, and niobium result in higher strength. Hot or cold working an alloy to obtain a finer
grain size typically increases tensile yield strength but decreases stress-rupture strength.

As discussed previously, properties of all age-hardenable superalloys are dependent on heat treatment. Alloys
like Pyromet Alloy X-750 and Waspaloy have two or more preferred heat treatments (see Table 2) depending on
whether the application requires better short-time tensile and fatigue properties or long-time creep and
stress-rupture properties. Examples of alternative heat treatments have been shown for Waspaloy and X-750
alloys but the reader should refer to manufacturers’ datasheets for a more complete listing of alternative heat
treatments for the other superalloys.

Other Properties – While tensile and creep-rupture are the most basic mechanical properties considered for
high-temperature applications, design criteria may also consider resistance to fatigue (low- and high-cycle),
crack growth, and wear/erosion. Hardness and hot hardness tests are sometimes used as a rough measure of
yield strength and wear/erosion.

Alloy Selection

Appendix D. Page 110 of 116.


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A simplified method known as the Carpenter Selectaloy® system can help designers and engineers select the
most suitable superalloy based on strength and maximum temperature requirements. Figures 3 and 4 contain
Selectaloy diagrams for the 15 superalloys discussed in this article. Yield strength (Figure 3) or stress-rupture
strength (Figure 4) increases vertically on the Selectaloy diagram, and temperature increases from left to right.
The alloys are shown multiple times on the diagrams since the alloys are useful over a range of temperatures.
The diagram can be used to estimate how the strength of an alloy decreases with temperature, but also how the
strength of different alloys compare at different temperatures.

Appendix D. Page 111 of 116.


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It should be noted that the alloys were positioned on the Selectaloy diagrams based on average strength values
representative of compositions and heat treatments commonly used for each alloy. An alloy’s relative position
could move up or down, left or right, with relatively minor modifications of composition, processing and heat
treatment. Temperature limits should be considered approximate. Therefore, while the Selectaloy diagrams are
useful tools to screen candidate alloys, they are not a substitute for a more detailed evaluation of the critical
properties required for an intended application.

Pyromet A-286 alloy is the most basic age-hardenable superalloy in terms of properties and cost. A-286 provides
the lowest strength levels, but still higher by a factor of two than other non-age-hardenable stainless alloys.
When increased strength or temperature resistance is required, higher nickel alloys are typically preferred. Alloys
with the highest levels of strength and temperature resistance typically contain the highest alloy contents and
significant levels of cobalt. Relative cost of these alloys will be discussed in the next section.

The Selectaloy diagrams presented in this article provide a method to compare basic strength properties and
temperature limitations of common wrought age-hardenable superalloys. However, alloy selection will
undoubtedly depend on many other considerations, including other physical and mechanical properties as well
as environmental resistance and cost. For example, Thermo-Span and Pyromet CTX-909 alloys provide a
benefit of much lower expansion during heating but at the expense of oxidation and corrosion resistance in the

Appendix D. Page 112 of 116.


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uncoated condition. Pyromet 31V and Pyromet 751 alloys provide similar strength and temperature resistance,
but the higher chromium content of 31V alloy results in much improved resistance to sulfidation and other forms
of hot corrosion.

Alloy Cost

From the user’s standpoint, alloy selection must be based on expected cost effectiveness.

In today’s competitive global environment, overdesign is less common. The trend is to select the lowest-cost
material to meet design requirements for the application. However, a higher-cost alloy may be justified to
minimize overall life cycle cost or for longer service of certain components in a system that is critical or too
expensive to be shut down for maintenance. Surely, knowledge of alloy capabilities is critical in making the best
decision.

As temperature and strength requirements increase, so does the necessary alloy content. Figure 5 compares the
relative alloying costs of the 14 alloys using Pyromet A-286 alloy as a base (cost factor of 1.0). The cost factors
are based on 10-year averages of the intrinsic alloying element costs at market prices. Higher temperature
strength and resistance typically require higher nickel and cobalt contents. Nickel and cobalt prices have
historically been volatile, with high and low prices varying by a factor of 4 to 5. More recently, the price of
molybdenum, a potent solid solution strengthener, has increased in price by a factor of nearly ten over the last
two years.

Appendix D. Page 113 of 116.


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As discussed above, the cost factors in Figure 5 are based only on raw material elemental costs (10-year
averages) that fluctuate significantly with time. Differences in melting, working, and other processing costs,
which can be substantial, are not included in these factors. Processing yields and specific end user requirements
(grain size, ultrasonic testing, etc.) significantly impact product cost. However, the cost comparisons are useful
because alloying costs typically represent a large portion of superalloy product cost. Since superalloys are
designed for high temperature strength and resistance to deformation, processing difficulty and cost also
increase with hot strength and maximum temperature capability.

Figure 6 shows the relationships of stress-rupture strength at 1200-1500°F (650-815°C) with raw material cost
factor. It is apparent that the alloys that provide higher levels of strength, temperature resistance, and/or
specialized properties also cost more, which reinforces the importance of the alloy selection process.

Appendix D. Page 114 of 116.


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More Technical Article:


http://crswnew.cartech.com/wnew/techarticles/TechLibrarySelector.html

Appendix D. Page 115 of 116.


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Microplasticity: 1 – dislocations
MSoM / MEM 2nd year. 6 lectures.
Steve Roberts

• The basics revisited. Burgers vector and Burgers circuit. Line sense and FS/RH convention. Geometry
of dislocations: edge, screw and mixed. Conservation of Burgers vector at nodes.
• Elastic properties of dislocations. Stress fields of screw and edge dislocations, strain energy of a
dislocation. The force on a dislocation. Forces between dislocations. Image forces. Small-angle grain
boundaries and epitaxial interfaces.
• Slip. Dislocation sources and multiplication. Climb and jogs.
• Strength of crystalline solids. The Peierls stress and lattice resistance. Kinks and thermally activated
glide. Temperature and strain-rate dependence of flow stress. Plastic strain due to dislocation
movement.
• Dislocations in c.c.p. metals. Perfect dislocations, Shockley partial dislocations and intrinsic stacking
faults. The Thompson tetrahedron. Lomer-Cottrell locks. Cross-slip. Frank partial dislocations.
• Dislocations in h.c.p. metals. Basal and non-basal slip.
• Dislocations in b.c.c. metals. Absence of stable stacking faults. Non-planar screw dislocation cores.
• Dislocations in ordered intermetallics. Superdislocations, antiphase boundaries and the yield stress
anomaly.
• Dislocations in non-metals. Ionic and covalent crystals.

Followed by “Microplasticity: 2 – strength of materials”

Steve Roberts – Microplasticity © S.G. Roberts 1: 1

Books and other Resources

• “Introduction to Dislocations”, D. Hull and D.J. Bacon (3rd edn.).

• “Theory of Dislocations”, J.P. Hirth and H. Lothe.

• “Dislocations”, J. Freidel.

• “Physical Metallurgy”, R.W. Cahn and P. Haasen.

• “Crystallography and Crystal Defects”, A. Kelly and G.W. Groves.

• “Worked Examples in Dislocations”, M.J. Whelan.

• “Physical Metallurgy Principles”, R.E. Reed-Hill (3rd edn.).

• “Microplasticity”: Lecture notes by A.P. Sutton, Materials Dept. Library.

Steve Roberts – Microplasticity © S.G. Roberts 1: 2

1
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Recap – Burgers vector

Perform an atom-to-atom circuit around the


dislocation line, returning to the start point.

Convention: choice of line direction is


l arbitrary, but having chosen it, the circuit is
done in the right-hand sense.

Repeat the atom-to-atom circuit in a perfect


crystal.
S F
Circuit does not close.
b Closure vector is the Burgers vector b.

Convention: b goes from Finish to Start of


the circuit.

Convention: “FSRH”
b is defined w.r.t. lattice of perfect crystal

Steve Roberts – Microplasticity © S.G. Roberts 1: 3

Edge dislocations – where is the half plane ?

Silicon Structures shown so far have been grossly


simplified, as simple cubic lattices.

In materials with more realistic structures, geometry


of even simple dislocations may be more subtle.

Silicon has a face centred cubic lattice, with two


atoms per lattice point.

In the High Resolution Transmission Electron


Micrograph shown, each bright spot represents one
lattice point.

There is an edge dislocation present.

However, these lines are only one way of indicating


lattice planes crossing the dislocation core.

“The extra half plane” concept isn’t quite as simple


as in the “simple cubic” case.

Nonetheless, the half plane is in both cases on the


same side of the slip plane.

Steve Roberts – Microplasticity © S.G. Roberts 1: 4

2
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Screw dislocations – more detailed geometry

l
n+¾ n+½
l

b
n+¼
n+0
b

b b The “standard picture” above makes it


appear that the dislocation is confined to one
plane (unless it reconstructs in some way).
n+¾ n+½
Real situation for a pure screw dislocation is
rather more like that to the left.

Displacement parallel to b accumulates


uniformly as one progresses round the core
of the dislocation.

n+0 n+¼ In real materials this “helical” structure gets


further complicated…

Steve Roberts – Microplasticity © S.G. Roberts 1: 5

Mixed dislocations
The Burger’s vector b is the principal defining For stress analyses, we can treat mixed
characteristic of a dislocation. dislocations as equivalent to a vector sum of pure
When a dislocation moves, every atom it crosses edge and pure screw components, which we can
on the slip plane moves by b. treat independently:
This happens whatever the line vector. bs
In many real materials, especially those with “soft” be bs
bonding, there is no preferred crystal direction for b
the dislocation line. be
Most dislocations will then not be pure screw or l b
pure edge, but somewhere in between – “mixed” θ
dislocations.
bs = b cos θ bs
l b
be = b sin θ
be

The reason we can do this is because the stress


fields of the edge and screw components are
M “orthogonal” – they have no components in
common.
S E

Steve Roberts – Microplasticity © S.G. Roberts 1: 6

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Dislocation nodes

b1
b3
1 b1
b1
1 3 b3
b2 3
2
b2

2 b1 b3

Since the only places the crystal structure is


b2
interrupted are at the dislocation cores, displacements
in the “Burgers circuits” 2 and 3 must add to give the
displacement associated with either of the two b1 = b2 + b3
variants of “Burgers circuit” 1.

b1 = b2 + b3

(N.B. care is needed with the senses of the line


vectors.)

Steve Roberts – Microplasticity © S.G. Roberts 1: 7

Dislocation loops

One type of dislocation loop forms the


boundary of a completely enclosed patch of
slipped material on the slip plane.

View down direction 1

b
b
l l
b
b
2
b b View down direction 2

1
Shear stresses acting on this loop will tend
either to expand or to contract it.
b must be the same at all points on the loop.

Steve Roberts – Microplasticity © S.G. Roberts 1: 8

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Electron microscopy of dislocations


Diffraction contrast in the T.E.M. is now the
commonest way of “seeing dislocations” and
Electron beam how they move and interact.

wavelength λ
An electron beam is “shone” onto a crystal so
that a Bragg condition is satisfied.

λ = 2d sin θ

A strong diffracted beam results, and illuminates


the imaging screen.

Near the core of the dislocation, the lattice


planes are bent.

The Bragg condition is no longer satisfied.

The diffracted beam is very weak or absent.

So in this “bright field” image the region near the


dislocation core appears dark.

Visiblity is due to the dislocation’s strain field.

Steve Roberts – Microplasticity © S.G. Roberts 1: 9

Some TEM pictures of dislocations

Dislocation
network in
graphite

(Amelinckx 1960)

10 µm

1 µm

Moving
Dislocation tangles in strained
dislocations in
stainless steel.
molybdenum
(Whelan, 1958)
(Robertson 1999)

Steve Roberts – Microplasticity © S.G. Roberts 1: 10

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Strains and Stresses around Dislocations

Dislocations have The elastic field controls how dislocations react


to “distant” microstructural features with their
• a long-range stress field that can be own elastic stress fields
analysed using linear elasticity - other dislocations
– diffuse strain energy stored in a large - mis-fitting precipitates
volume - mis-fitting solute atoms
– no variation with core position relative - twins
to atomic structure - applied stresses

• a core within which the strains are too great The core structure controls how the dislocation
to be treated using linear elasticity interacts with the crystal’s lattice & atomic
– intense strain energy stored in a small structure:
volume - dislocation dissociation
– may be large energy fluctuations with - core spreading
core position - mobility
- cross-slip
- defects on the core (kinks and jogs)
- details of interaction with point defects

Steve Roberts – Microplasticity © S.G. Roberts 1: 11

Elasticity - recap

Displacement vector: Stress tensor: σ xx = 2Gε xx + λ∆


u = [ux, uy, uz]
σ yy = 2Gε yy + λ∆
Strain tensor:
∂u x σ zz = 2Gε zz + λ∆
ε xx =
∂x σ xy = 2Gε xy
 ∂u ∂u y  σ xz = 2Gε xz
ε xy = 21  x + 
 ∂y ∂x  σ yz = 2Gε yz
etc.
2Gν
Dilatation, ∆: λ=
∆ = εxx+ εyy+ εzz (1 − 2ν )
z Elastic energy:

dE el = 21 dV ∑ ∑σ ε
i= x,y,z j= x,y,z
ij ij

y
x

Steve Roberts – Microplasticity © S.G. Roberts 1: 12

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Strain field of straight screw dislocation


z
ε xx = ε yy = ε zz = ε xy = ε yx = 0
∂uz b ∂ y
ε xz = 1
2
= tan −1 
∂x 4π ∂x x
x θ
b 1 y
y =−
( x)
4π 1 + y 2 x 2
b y b sin θ
=− =−
b 4π x 2 + y 2 4π r

“Recipe” : ∂u z b ∂ y
- take a hollow cylinder, axis along z: ε yz = 1
2
= tan −1 
- cut on a plane parallel to the z-axis; ∂y 4π ∂y x
-displace the free surfaces by b in the z-direction. b 1 1
=
By inspection: u = u = 0
x y
4π 1 + y( x)2
x
b x b cos θ
bθ = =
uz = 4π x 2 + y 2 4 π r

b y
= tan −1 
2π x
Steve Roberts – Microplasticity © S.G. Roberts 1: 13

Stress field of straight screw dislocation


ε xx = ε yy = ε zz = ε xy = ε yx = 0 In Polar coordinates:
b y b sin θ
ε xz =− =− (either by direct inspection, or by transforming the
4π x 2 + y 2 4π r strains and stresses from Cartesian co-ordinates)
b x b cos θ b
ε yz = = ε θz = ε zθ = All other components of
4π x 2 + y 2 4π r 4πr the stress tensor are zero.
Gb
σ θz = σ zθ =
2πr
σ xx = σ yy = σ zz = σ xy = σ yx = 0
Note:
∆=0 • Stress and strain fields are pure shear
Gb y Gb sin θ • Fields have radial symmetry
σ xz = 2Gε xz = − =− • Stresses and strains are proportional to 1/r:
2π x 2 + y 2 2π r
• extend to infinity
Gb x Gb cos θ • tend to infinite values as r⇒0
σ yz = 2Gε yz = =
2 π x 2 + y 2 2π r
Infinite stresses cannot exist in real materials:
the dislocation core radius r0 is that within which
our assumption of linear elastic behaviour breaks
down. Typically r0 ≈ 1 nm.

Steve Roberts – Microplasticity © S.G. Roberts 1: 14

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Stress field of straight edge dislocation


z
σ xz = σ zx = σ yz = σ zy = 0
3x 2 + y 2 Gb
σ xx = −D y , with : D =
(x 2
+y 2 2
) 2π(1 − ν )

x2 − y2
σ yy = D y
(x 2
+ y2 )
2

y x2 − y2
σ xy = σ yx = D x
x (x 2
+ y2 )
2

“Recipe” : σ zz = ν( σ xx + σ yy )
- take a hollow cylinder, axis along z:
- cut on a plane parallel to the z-axis;
- displace the free surfaces LMNO by b in Hydrostatic Stress, P :
the x-direction. 2(1 + ν ) y
P = − 31 (σ xx + σ yy + σ zz ) = D 2
Situation is plane-strain. No displacements 3 x + y2
in z-direction.
Note:
Derivation of stress tensor is complicated. • Stress and strain fields are not pure shear
• Stresses and strains are proportional to 1/r:
(see Hirth and Lothe for the full works) • extend to infinity
• tend to infinite values as r⇒0
Steve Roberts – Microplasticity © S.G. Roberts 1: 15

Stress field around edge dislocation

y
+ -
400-500 -
300-400 x
200-300
100-200
0-100
- +
-100-0
-200--100
-300--200
-400--300
+
-500--400 + -

Shear stress σxy around an Hydrostatic stress

+ - edge dislocation with b = bx (σxx + σyy + σzz) /3


around an edge dislocation
(arbitrary units) with b = bx

(arbitrary units)

Steve Roberts – Microplasticity © S.G. Roberts 1: 16

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Strain energy of a screw dislocation

Elastic energy per unit volume =


e
c or 1 2
(εθzσθz + ε zθσzθ ) = Gb 2
2 8 πr

r Volume of shell, thickness δr = 2πr.δr


b

Elastic energy of shell = Gb2


δr
4 πr
In the shell shown,
b R
ε θz =ε zθ = Gb2
4 πr Total elastic energy = ∫ 4πr dr
r0
Gb
σθz = σ zθ = Gb 2  R 
2 πr = ln 
4π  r0 

All other stresses and strains are zero. per unit length of
dislocation line

Steve Roberts – Microplasticity © S.G. Roberts 1: 17

Strain energy of an edge dislocation


Now imagine making the dislocation by cutting on
green plane and displacing the two sides by relative b
b
Gb
e
c or 2π(1 − ν )x
y
σxy
x

0
displacement b
with dislocation in place,
Work done at x
Gb x2 − y2 =
1 Gb
b
σ xy = σ yx = x
(
2π(1 − ν ) x 2 + y 2 2 ) 2 2π(1 − ν )x
Total work done between r0 and R
at y = 0 : R
Gb 2
σ xy =
Gb = ∫ 4π(1 − ν)x dx
2π(1 − ν )x r0
R This must equal the
Gb 2
= ln  elastic energy per unit
4π(1 − ν )  r0  length of the dislocation.

Steve Roberts – Microplasticity © S.G. Roberts 1: 18

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Core energy & total energy of dislocations


We can estimate the “core energy” as To estimate the elastic energy
equivalent to about one broken bond per atom
spacing along the core. Gb 2  R 
Eel = ln 
This will be about 4π( α )  r0 
(vacancy formation energy)/(co-ordn. no.) :
We need values for R and r0:
typically (1 - 3 eV) / (4 – 12) per 0.2 – 0.3 nm
“reasonable” values are R ~ 1 µm, r0 ~ 1nm:
So range is likely to be 0.5 – 5 eV nm-1 . 1 R
= 0.1 – 1 nJ m-1 ln  ≈ 0.5
4π( α )  r0 
This energy is for the “relaxed state”. Gb 2
Eel ≈
2
If we try to move the dislocation, the core
energy will fluctate as the dislocation goes Typically G = 60 – 120 GPa, b = 0.2 – 0.3 nm:
from one relaxed state to the next one.
Eel will be in range 1 – 4 nJ m-1.
This is the origin of the “Peierls – Nabarro
stress” – the minimum stress to move the So total energy of dislocation is likely to be
dislocation line. (see later) (just) dominated by the diffuse elastic energy –
but energy fluctuations will depend on the core
term.

Steve Roberts – Microplasticity © S.G. Roberts 1: 19

Force on an (edge) dislocation

Edge: glide Edge: climb


If there is a high enough shear
stress component in the direction of
b, then the dislocation can glide.

If there is a dilatational stress


parallel to b, then if temperature is
high enough for vacancies to
diffuse to or from the dislocation, it
will climb.

In both cases the applied stress


does work in changing the shape of
the crystal.

This is achieved by the motion of


the dislocation, which responds as
if the stress is applying a force to it.

This “configurational force” is


defined by the rate of change of
energy of the system as the
dislocation moves.
“conservative motion” “non-conservative motion”

Steve Roberts – Microplasticity © S.G. Roberts 1: 20

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Force on a dislocation

If section of dislocation line moves by δs, then within area


δsδl, all atoms “above” the slip plane are displaced by b
w.r.t. all those “below”.

τ F Work done, δW = force.displacement


= stress.displacement x area
= τ.b δsδl
b l
Force on dislocation (the “Peach-Koehler” force) is defined
as work done per unit length of dislocation line when it
glides unit distance.
l
δl
δs Force, F = work done / line length / glide distance
= δW / (δs δl)
= τ.b

Dislocation line can only meaningfully If the full stress tensor σ is used, then: F = (σb) × l
move normal to the line vector l.
 Fx   σ xx τ xy τ xz  b x   l x 
F must be perpendicular to l       
 Fy  =  τ yx σ yy τ yz  b y  ×  l y 
F   τ τ zy

σ zz  b z   l z 
 z   zx
Steve Roberts – Microplasticity © S.G. Roberts 1: 21

Forces on dislocations

Dislocation motion only has “meaning” Forces on dislocations can only act normal to the
normal to the line vector. line vector.

Screw Mixed Loop

τ
F
F τ τ

b b
b

Steve Roberts – Microplasticity © S.G. Roberts 1: 22

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Forces between dislocations

Using arguments based on dislocation


energetics, it is easy to see that, for
dislocations of same line vector on the same
Gb 2 Gb 2
Eel ≈ 2 Eel ≈ 2 slip plane, dislocations with opposite b attract
2 2 each other, dislocations with identical b repel.

-b b b b
The elastic energies of the separated
dislocations given apply strictly only as r ⇒ ∞.
r r
As r decreases, energy changes towards the
“overlap” values. (see question sheet 1).

2b
0

G( 2b)2 This is one view of the reason for the forces


Eel = 0 Eel ≈ = 2Gb 2 between dislocations.
2
dEel dE el For more complicated situations, it is easier to
F= <0 F= >0
dr dr see the force as being due to the local stress at
each dislocation.

Steve Roberts – Microplasticity © S.G. Roberts 1: 23

Forces between screw dislocations


y 1
Force on dislocation 2 from dislocation 1, resolved
x
onto the glide plane is:

z b 2 Gb 2
Fres = cos θ
θ 2πr
∆y r b
Alternatively, we can use the stress field
expressed in Cartesian co-ordinates:
∆x
σ xx = σ yy = σ zz = σ xy = σ yx = 0
Dislocation 2 “feels” the stress field Gb ∆y Gb sin θ
of dislocation 1 (and vice versa). σ xz = − =−
2π ∆x 2 + ∆y 2 2π r
Gb Gb ∆x Gb cos θ
σ θz = σ zθ = σ yz = =
2πr 2π ∆x 2 + ∆y 2 2π r
So force on dislocation 2 from
dislocation 1 is:
Note that the shear stress acting to shear atoms
Gb 2 parallel to b above and below the glide plane is σyz.
F=
2πr Gb 2 Gb 2 ∆x
Fres = σ yzb = cos θ =
… but this force acts in the radial direction. 2πr 2π ∆x 2 + ∆y 2

Steve Roberts – Microplasticity © S.G. Roberts 1: 24

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Forces between edge dislocations


y 2
3∆x 2 + ∆y 2 Gb
x σ xx = −D y , with : D =
z
b
(∆x 2
+ ∆y 2 2
) 2π(1 − ν )

∆x 2 − ∆y 2
σ xy = σ yx = D ∆x
∆y
b
r (∆x 2
+ ∆y 2 )
2

θ
1 ∆x So glide force, resolved onto the slip plane, is:

Dislocation 2 “feels” the stress field of Gb2 ∆x( ∆x 2 − ∆y 2 )


Fglide =
dislocation 1 (and vice versa).
(
2π(1 − ν ) ∆x 2 + ∆y 2 2 )
The important components of the
stress field are: 0.3

σxy – produces glide force on disln 2;


Fglide
σxx – produces climb force on disln 2. 0
Gb 2 2 4 6 8
2π(1 − ν )∆y ∆x / ∆y

-0.3

Steve Roberts – Microplasticity © S.G. Roberts 1: 25

Stable arrangements for edge dislocations

0.3 For like Burgers vectors:


∆x = ±∆y: unstable equilibrium
∆x = 0 : stable equilibrium
Fglide
0 For opposite Burgers vectors:
Gb 2 2 4 6 8 ∆x = ±∆y: stable equilibrium
2π(1 − ν )∆y ∆x / ∆y ∆x = 0 : unstable equilibrium

-0.3
For a set of “opposite” Burgers vectors:

There are a large number of possible stable


arrangements.
For like Burgers vectors:
Stable array is a planar
stack

A low angle tilt boundary.

This arrangement has a


“Taylor lattice” “Dipole dispersion”
strong long-range stress
field.
These stable arrangements have minimal long-
range stress fields.
Steve Roberts – Microplasticity © S.G. Roberts 1: 26

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Dislocations near free surfaces: image forces

y
x

σxx around edge dislocation The “trick” is to introduce a virtual dislocation (of opposite b)
which is the mirror image in the free surface of the real one.
If dislocation is near free
surface, it produces stresses The combined stress fields of the real and image dislocations
in the surface plane that the reproduce the solution for the stress field of the dislocation
surface cannot support. near the free surface.

Stress field must be modified The real dislocation “sees” the stress field of the image
by presence of free surface. dislocation and is attracted to the free surface.

Steve Roberts – Microplasticity © S.G. Roberts 1: 27

Dislocation line tension


The energy per unit length of the dislocation
line is equivalent to a line tension: On small dislocation line segment, length δl
Units: J m-1 = (N m) m-1 = N Line tension exerts force:
Strength ≈ Gb2/2 2 (Gb2/2 sin(δθ/2) )
= Gb2/2 sinδθ
A straight dislocation line will exert an inward = Gb2δθ/2
force equal to the (line energy / length) on any
pinning points. Applied shear stress exerts force
τ.b δl = τ.b Rδθ
A curved dislocation line will have a tendency
to straighten itself between any two points, as These must balance:
this minimises line length and therefore energy.
Gb2δθ/2 = τ.b Rδθ
F Gb2/2
τ.b = Gb2 / 2R

R or if we only take component of τ in direction of b:


b
F δθ/2
δl τ = Gb / 2R
δθ/2
R Stress required to move a dislocation line
F increases as its radius of curvature decreases.
τ
Gb2/2

Steve Roberts – Microplasticity © S.G. Roberts 1: 28

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Dislocation sources

The Frank-Read source is the most


commonly illustrated type of
dislocation source.

Imagine a segment of dislocation


F F
F line pinned at two ends – probably at
F large “kinks” (see later).
F b
Apply a shear stress τ which has a
component in the direction of the
dislocation’s Burgers vector b.

Dislocation line will be subjected


to the Peach-Koehler force F.

τ If F is greater than the minimum


level needed to make the dislocation
glide plus the effects of line tension,
the dislocation will glide, in the
direction of F.

Steve Roberts – Microplasticity © S.G. Roberts 1: 29

Dislocation sources

Increasing τ is needed as the


dislocation “bows out”, because
b the line curvature increases.
At this stage, when the loop shape
is a half-circle, dislocation
curvature is a maximum.
Now no increase in stress is
needed to keep the dislocation
moving – the loop is unstable.
b The dislocation line is now
b expanding “behind” its original
position.
l These segments are of opposite
l
sign. They attract one another.
τ The two “rear” segments
approach each other rapidly

Steve Roberts – Microplasticity © S.G. Roberts 1: 30

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Dislocation sources

Increasing τ is needed as the


dislocation “bows out”, because
b the line curvature increases.
At this stage, when the loop shape
is a half-circle, dislocation
curvature is a maximum.
Now no increase in stress is
needed to keep the dislocation
b moving – the loop is unstable.
The dislocation line is now
expanding “behind” its original
position.
These segments are of opposite
b sign. They attract one another.
τ The two “rear” segments
approach each other rapidly
and mutually annihilate.

Steve Roberts – Microplasticity © S.G. Roberts 1: 31

Stress to operate dislocation sources

Increasing τ is needed as the


dislocation “bows out”, because
the line curvature increases.
At this stage, when the loop shape
is a half-circle, dislocation
curvature is a maximum.
b

τ.b = Gb2 / 2R

2R
or if we only take component of τ
in direction of b:

τ = Gb / 2R
τ

Steve Roberts – Microplasticity © S.G. Roberts 1: 32

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Real dislocation sources

The “classic” Frank-Read source. “Half sources” where a single pinning point is near
a grain boundary, can act as dislocation “mills”.
Silicon. (C. Dash, 1957 )
Molybdenum (bcc). (I. Robertson, 1999)
Note the alignment of dislocation segments along
<110> directions. Anisotropy of Peierls stress Note the very different mobilities of the screw
controls loop shape. segments (slow) and edge segments (very fast) of
the same loop. Loop shape is controlled by this
The dislocation lines leaving the slip planes at the mobility difference.
pinning points are also visible.
Steve Roberts – Microplasticity © S.G. Roberts 1: 33

Widening of slip band by multiple cross-slip

Screw dislocation can have high enough


resolved shear stress for glide on more
than one slip plane.

Cross-slip can occur.

But this leaves some segments of


dislocation on the original (“primary”) slip
plane.

Dislocation can cross-slip back on to a


parallel primary slip plane, where it forms
a new dislocation source.

… and the process can repeat.

Steve Roberts – Microplasticity © S.G. Roberts 1: 34

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Widening of slip band by multiple cross-slip

Glide band widening in LiF

original dislocations

Glide band width after first loading

Glide band width after second loading

Steve Roberts – Microplasticity © S.G. Roberts 1: 35

Strain rate from motion of dislocations


d
w If a dislocation moved the whole length of the crystal d, it
τ would contribute b to the displacement D.

If each dislocation moves an amount xi (less than d),


then each will contribute ( xi / d ).b to D.
b
h D= ∑ xi
d i

D b
Shear strain is: ε= = ∑ xi
h dh i
τ b

D 1
Define average distance
moved by each dislocation:
x= ∑ xi
N i

Density of mobile N
dislocations is: ρm =
hd
xi
dε dx
Strain rate: ε& = = b ρm = bρm v
dt dt

- where v is the average dislocation glide velocity.

Steve Roberts – Microplasticity © S.G. Roberts 1: 36

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Dislocation motion – The Peierls-Nabarro Stress


Elasticity theory tells us a lot about dislocations’ w?
stresses, energetics & interactions, but to
understand dislocation mobility we need to look
at the core structure and how it changes as the
dislocation moves.

1. Can we define the width of a


dislocation core and what does it
depend on?

2. What happens as the dislocation


moves on the glide plane?

3. Why do dislocations choose particular


crystallographic planes within a crystal
on which to glide?
In principle slip could take place on N.B. – the P-N approach only applies to
any plane. dislocations with planar cores.

4. Why are the Burgers vectors of perfect (e.g. edge dislocations, dissociated screw
dislocations usually the shortest dislocations)
available crystal lattice vectors?
In principle they could be any crystal Structure of pure screw dislocation cores
lattice vector. (E = Gb2/2 is one factor) (e.g. in bcc metals) needs direct atomistic
simulation.

Steve Roberts – Microplasticity © S.G. Roberts 1: 37

Core width – bubble raft

Steve Roberts – Microplasticity © S.G. Roberts 1: 38

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Dislocation core width

Steve Roberts – Microplasticity © S.G. Roberts 1: 39

Definition of core width


y
b
Consider displacements of lattice
uB with dislocation present w.r.t. lattice
A with dislocation absent.
a x Above and below the slip plane
B these displacements u will be
uA different at the same distance x
from the centre line of the
dislocation.
∆u / b
The disregistry ∆u is the difference
between these displacements.
+0.5
∆u = uB - uA
+0.25
w x
Width w of core can now be defined
-0.25 as the width of the region within
which ∆u is greater than half its
-0.5
maximum value (0.5b)

Steve Roberts – Microplasticity © S.G. Roberts 1: 40

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Core types

wide narrow dissociated

0.5 0.5 0.5

∆u / b ∆u / b ∆u / b
x

-0.5 -0.5 -0.5

f f f
Area = b Area = b Area = b/2

0 0 0
x x x

d ∆u
f(x) = - the distrubution of Burgers vector along the slip plane.
dx

Steve Roberts – Microplasticity © S.G. Roberts 1: 41

Peierls energy and Peierls stress


y
b
Find that energy fluctuates, with period b/2:
uB
A Ep  4 π∆x 
a
E = E0 + sin 
x 2  b 
B
uA Gb 2  − 2πw 
Ep = exp  Peierls Energy
π(1 − ν )  b 
Assume that
1) The atoms in plane A interact with
the atoms in plane B via a simple Maximum force needed is maximum slope of
sinusoidally-varying force law. energy / displacement curve:
2) Disregistry forces are balanced by
elastic stresses from material above
and below the slip plane 2Gb  − 2πw 
Fmax = exp 
…. gives an analytical solution for w: (1 − ν )  b 
a Stress to move dislocation = Fmax / b:
w= (edge )
(1 − ν )
= a (screw) 2G  − 2πw 
τp = exp  Peierls Stress
… then calculate the dislocation energy as
(1 − ν )  b 
sum of disregistry energy and elastic energy,
as function of core position ∆x w.r.t. lattice.
Steve Roberts – Microplasticity © S.G. Roberts 1: 42

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“Peierls valleys”

2G  − 2πw  The Peierls energy varies with dislocation


Peierls Stress τp = exp 
(1 − ν )  b  orientation w.r.t. the lattice.

Consequences: Dislocations tend to lie along directions where Ep is


lowest – “Peierls valleys”
• Dislocations with wide, planar cores are easier (esp. in strongly-bonded materials)
to move than ones with narrow (or even non-
planar) cores. [110]

– edge dislocations will have lower τp than screw


dislocations (esp. in bcc – see later)
[101]
• Dislocations with widely-spaced slip planes will
have wider cores [011]
Assumption of Peierls model is that dislocations
– hcp metals with high c/a will have low τp
move “wholesale” from one Peierls valley to the
next.
• Dislocations with small b will have low τp.
Also – no thermal
• These effects are strong, as they are via an activation. τp =
exponential relationship. stress to move at
absolute zero.

Steve Roberts – Microplasticity © S.G. Roberts 1: 43

“Peierls valleys”, kinks and dislocation glide


At real temperatures, dislocation Dislocation lines can move under stress by nucleation
lines have a population of kinks in and sideways propagation of “double kinks”
thermal equilibrium.

Kink formation is opposed by line tension and the


mutual attraction of kinks of opposite sign.
Ep
Thermal activation is needed.
Steve Roberts – Microplasticity © S.G. Roberts 1: 44

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1 2 3
Crystallography of kinks
Kink also have structure – they will have lowest energy if
aligned along “secondary Peierls valleys”. (1)

However, this gives maximum line length – maximum line


energy.

Minimum line energy configuration is to have dislcoation


line and kinks “ignoring” the primary and secondary
Peierls valleys. (2)

Real dislocation structure will be a compromise, giving


minimum total energy (3).

Balance will depend on bonding strength and temperature.

Stress to produce glide at given rate will then depend on:

1. Stress to produce double kinks;


2. Stress to move kinks

These will depend on the details of the kink structure


(material & temperature dependent) and the amount of
thermal activation available (temperature dependent).

Theories have been worked out in detail (see Hirth and Lothe), but are
beyond the scope of this course. We will look at simplified theories
which ignore the “kink mechanics”.
Steve Roberts – Microplasticity © S.G. Roberts 1: 45

Kinks from dislocation intersections

The intersection of these two dislocations dislocations leads to


the formation of a kink on one dislocation.

The kink is effectively an atomic-length section of edge


dislocation:
- on the same crystal glide plane as the rest of the dislocation;
- acts as a “secondary dislocation”
- sideways motion of the kink can act as mechanism for glide
of the main dislocation

Steve Roberts – Microplasticity © S.G. Roberts 1: 46

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Jogs from dislocation intersections

The intersection of these two screw dislocations


leads to the formation of a jog on each one.

The jog is effectively an atomic-length section of


edge dislocation:
- probably on a non-glide crystal plane;
- can only move with dislocation to which it is
attached by climb.

Steve Roberts – Microplasticity © S.G. Roberts 1: 47

Jogs from dislocation intersections

The intersection of these two dislocations dislocations leads


to the formation of a jog on one dislocation.

The jog is effectively an atomic-length section of edge


dislocation:
- in this case on a crystal glide plane;
- can move with dislocation to which it is attached by glide.

Steve Roberts – Microplasticity © S.G. Roberts 1: 48

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Climb and jogs

σxx l σxx

Mechanical driving force: work is done by the


applied stress as the dislocation climbs.
F = b σxx (or full P-K for more complex stress states)

Vacancy diffusion to or from edge dislocations


will cause them to “climb” . l
In the absence of a driving force, there will be
equal diffusion rates to and from the
dislocation’s core – no net climb.
“Chemical” driving force: excess vacancy
concentration in crystal. Dislocation core can
act as vacancy sink.

Steve Roberts – Microplasticity © S.G. Roberts 1: 49

Climb and Jogs

σxx σxx

etc.

Climb will not occur uniformly along the dislocation line.

Each vacancy that “lands” creates a pair of unit-height jogs.

Line tension forces and mutual elastic attraction of the posistive and negative jogs will
provide forces tending to remove them (removal still needs vacancy absorption or
emission)

The climb process can be visualised in terms of the creation, sideways diffusion and
recombination of jogs.

Jogs can also be created by dislocation intersections, and can be strong pinning points
opposing dislocation glide.

Steve Roberts – Microplasticity © S.G. Roberts 1: 50

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Dislocations in cubic close-packed metals


Close packed cubic pure metals:

aluminium, copper, nickel,


lead, silver, gold, palladium

Alloy systems with close packed cubic phase:

aluminium alloys, α-brass, (some) stainless


steels, nickel-based alloys

N.B. –these are often called “f.c.c. metals”: while


this is a valid description (the lattice type is face-
centred cubic) it can lead to confusion.

Cubic closed packed metals (“face- Other materials have a f.c.c. lattice but are not
centred cubic”) have intersecting close packed. (e.g. Si, Ge, C). There are several
close-packed {111} glide planes. similarities in dislocation structure and behaviour
between the f.c.c. metals and the covalent f.c.c.
Close packed directions are <110>; materials, but also many differences.
Burgers vectors a/2 <110>

Peierls valleys (weak) along <110>

Steve Roberts – Microplasticity © S.G. Roberts 3:1

Cubic close-packed metals

[001]
Unit cell, looking down onto the (111) plane.
[001] [010]

[100] [010]

[100]

Steve Roberts – Microplasticity © S.G. Roberts 3:2

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Cubic close-packed metals

[001]
Unit cell, looking down onto the (111) plane.

<110> slip directions on this plane.

[110]

[011] [101]
[100] [010]

(111)

Steve Roberts – Microplasticity © S.G. Roberts 3:3

Cubic close-packed metals

[001]
Unit cell, looking down onto the (111) plane.

<110> slip directions on this plane.

a/2 <110> perfect Burgers vectors on this plane.

a
2 [110]

a
a [101]
[011] 2
2

[100] [010]

Steve Roberts – Microplasticity © S.G. Roberts 3:4

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Cubic close-packed metals

[001]
Unit cell, looking down onto the (111) plane.

<110> slip directions on this plane.

a/2 <110> perfect Burgers vectors on this plane.

a a/6 <211> partial Burgers vectors on this plane.


2 [110]

a a
a [101]
2
[011] 2 2 [110]
a
a [211]
[121] 6
[100] [010] 6

a
6
[112] a
a [101]
[011] 2
2

Steve Roberts – Microplasticity © S.G. Roberts 3:5

Dissociation of dislocations in ccp metals

The “perfect” a/2<110> Burgers vector moves The “partial” a/6<211> Burgers vector moves
atoms in the upper layer to positions occupied by atoms in the upper layer to positions not normally
other atoms in the same layer – occupied by atoms in either of the layers shown.

The crystal structure is unchanged by the The crystal structure is changed by the passage
passage of a dislocation with this Burgers vector; of a dislocation with this Burgers vector, which is
the dislocation displaces atoms by a whole not a whole lattice vector.
lattice vector.
A Stacking Fault is produced. Another partial
dislocation is needed to remove the stacking
fault.
Steve Roberts – Microplasticity © S.G. Roberts 3:6

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Dissociation of dislocations – stacking faults

Perfect a/2<110> Burgers vector: Partial a/6<211> Burgers vector:

The green layer has been displaced by the The green layer has been displaced by the
passage of a perfect dislocation, carrying with it passage of a perfect dislocation, carrying with it
the orange layer above it . the orange layer above it .

Note the 3-layer stacking repeat (“ABC….”), Note the local 2-layer stacking repeat (“ABA”),
normal for the ccp structure. characteristic of the hcp structure.

No energy change. Higher energy.

Steve Roberts – Microplasticity © S.G. Roberts 3:7

Motion of partials & stacking fault

The picture shows just the two layers either


side of the active slip plane.

In both the animation and the picture, all the


distortions are drawn confined to one atomic
The animation shows just the two layers plane.
either side of the active slip plane.
In reality, the distortions will be (nearly)
A pair of partial dislocations pass between equally distributed around the dislocation
these two planes. lines, and will decrease with distance from
the dislocations.
The first partial moves atoms into faulted
positions; the second moves the atoms into These distortions are the dislocations’ strain
normal positions (but translated from their fields.
original positions by a/2<110>)

Steve Roberts – Microplasticity © S.G. Roberts 3:8

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Energetics of partials & stacking fault


(111)
The stacking fault has a higher energy
than the normal crystal structure – so
why is is there at all ?

The partial dislocations bounding it have


a combined energy lower than that of
the perfect dislocation.

Gb 2
E≈
2 b = a6 [2 1 1] b = a6 [1 2 1]
Partial dislocations:
⎛ G ⎛ a ⎞2 ⎞
E ≈ 2⎜ ⎜ ⎟ [12 + 22 + 12 ] ⎟ b = a2 [1 1 0]
⎜ 2 ⎝6⎠ ⎟
⎝ ⎠
Ga 2
= The energy calculations for the partial dislocations assume
6 that the partials are completely separated (I.e. stacking
fault is infinitely wide)
Perfect dislocation:
2
G⎛a⎞ 2 2 As stacking fault width increases (and stacking fault energy
E≈ ⎜ ⎟ [1 + 1 ] per unit length of line increases), dislocation energy
2 ⎝2⎠ decreases from Ga2/4 to Ga2/6.
Ga 2
=
4
Steve Roberts – Microplasticity © S.G. Roberts 3:9

Energetics of partials & stacking fault


Energy / length
Criteria for dissociation:

2
Ga r gy 1. a stacking fault structure of low energy
ne 2. partial dislocations bounding the stacking
4 ale
t ot fault which are of lower combined line
energy than the perfect dislocation.
y
Ga 2 dislo rg
catio
n ne In ccp metals both these criteria are met.
6 energ
y ult e
fa

Since the geometry of the close-packed plane


d means that the angle between the partials must
be 120º, we can see by inspection that Σb2 for the
Separation of Partials partial dislocations must be less than b2 for the
perfect dislocations.
There is a minimum in the energy of the
system at a non-zero fault width, d.

This is because the stacking faults between b = a6 [2 1 1] b = a6 [1 2 1]


a/6<211> dislocations in ccp metals are of 120º
relatively low energy. (e.g. Cu: 70 mJ m-2)
b = a2 [1 1 0]
This is because the ccp and hcp structures
are very similar, and because bonding in close
packed metals is largely non-directional.
Steve Roberts – Microplasticity © S.G. Roberts 3:10

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Stacking faults and partial dislocations: forces


(111)

At equilibrium spacing, d, forces must balance:

1. attractive force, = γ (stacking fault energy / unit area)


2. repulsive force F between dislocations (varies with d)

Approximate treatment:

b = a6 [2 1 1] b = a6 [12 1] Gb 2
F≅ (treats partials as ⏐⏐ screws)
4πd
Gb 2
At equilibrium: =γ
4πd
F γ γ F 4πγ
d=
Gb 2

For copper, G = 48 GPa, γ = 70 mJm-2,, b = 0.26 nm,


d
giving d ≈ 3.7 nm.

(See Qsheet 2 for more exact treatment)

Steve Roberts – Microplasticity © S.G. Roberts 3:11

Partial dislocations and stacking faults: images

Bubble raft

500 nm

Cu – 7% Al
HREM (Si)

Triple
junction
in AlN
[N.B. - most of these
images are not from
250 nm ccp metals!]
Steve Roberts – Microplasticity © S.G. Roberts 3:12

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Building Thompson’s Tetrahedron

[001]
Unit cell, looking down onto the (111) plane.

<110> slip directions on this plane.

a/2 <110> perfect Burgers vectors on this plane.

a a/6 <211> partial Burgers vectors on this plane.


2 [110]

a a
a [101]
2
[011] 2 2 [110]
a
a [211]
[121] 6
[100] [010] 6

a
6
[112] a
a [101]
[011] 2
2

Steve Roberts – Microplasticity © S.G. Roberts 3:13

Thompson’s tetrahedron
All possible slip planes and dislocations can be
[001] conveniently represented on a tetrahedron.

Faces (a,b,c,d): slip planes;


a Edges (AB, etc.): perfect Burgers vectors
[101] Peierls valleys
2
(111): c Vertex-centre (Aδ, δB, etc):
Shockley partial dislocations
a
A 2 [110] B
(111): a
a
[011]
2
(111): b a
B
a
D
a A 2 [110]
[011] [101]
2 2 a
a [211]
[121] 6
[010] 6
[100]
a δ
[110] (111): d a
2 [112]
a 6 a
C [011] [101]
2 2

Steve Roberts – Microplasticity © S.G. Roberts 3:14

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Make your own Thompson’s tetrahedron…

B
A

B
A

A B

Puzzle: one direction is


wrongly indexed !
C
(by Hirth & Lothe…)

D
C

C
D

Steve Roberts – Microplasticity © S.G. Roberts 3:15

Partial dislocations and the Thompson Tetrahedron


b?
B
A

The partials have to pass through the structure in D


the correct order to create this intrinsic stacking
fault. C

(If the partials act in the other order, a high- If we have an edge dislocation on the ABC plane
energy fault would result.) with l in the Cδ direction, is b = AB or BA ?
This will be important if we are considering
dislocation reactions – we have to know which
partial dislocations will meet of the 4 possible
combinations.
Steve Roberts – Microplasticity © S.G. Roberts 3:16

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FSRH Convention and dissociation order


We use the FSRH Convention, so if the dislocation
has its extra half-plane “outside” the ABC (111)
l plane, then b = BA.

This will split into Bδ and δA.


FSRH
The dissociation order rule is then:
b Convention
“Imagine you are standing on the outside of the
B
b tetrahedron looking down the dislocation line in the
A sense of the line vector. The “Greek-Roman”
partial is on your left, and the “Roman-Greek” on
your right.”
δ So, in this case:


δA

BA
D
Cδ Cδ

C

Steve Roberts – Microplasticity © S.G. Roberts 3:17

Lomer-Cottrell lock

Two dislocations with the same line vector CD, but


each gliding on its own plane.

B Dislocation 1: l = CD, b1 = BC
A Splits into Bα and αC

Dislocation 2: l = CD, b1 = CA
Splits into Cβ and βA

Use the “ordering rule”.

α
β

b2
b1
D

Steve Roberts – Microplasticity © S.G. Roberts 3:18

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Lomer-Cottrell lock

Two dislocations with the same line vector CD, but


each gliding on its own plane.

B Dislocation 1: l = CD, b1 = BC
A Splits into Bα and αC

Dislocation 2: l = CD, b1 = CA
Splits into Cβ and βA

Use the “ordering rule”.


αC


βA
D

Steve Roberts – Microplasticity © S.G. Roberts 3:19

Lomer-Cottrell lock

Two dislocations with the same line vector CD, but


each gliding on its own plane.

B Dislocation 1: l = CD, b1 = BC
A Splits into Bα and αC

Dislocation 2: l = CD, b1 = CA
Splits into Cβ and βA

Use the “ordering rule”.

α Reaction will give βA + Bα = ½BA along CD.


β
Cβ This is a low energy dislocation (b = ¼a[110]).

αC - The reaction will give rise to a stable product.


D
βA + Bα There is no glide plane containing BA and CD.
C
- The stable product is an immobile dislocation

Steve Roberts – Microplasticity © S.G. Roberts 3:20

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Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A

α
β

b = DC

Steve Roberts – Microplasticity © S.G. Roberts 3:21

Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A
Splits into two partials:

DC ⇒ Dα + αC

α
β

Steve Roberts – Microplasticity © S.G. Roberts 3:22

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Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A
Splits into two partials:

DC ⇒ Dα + αC

Following the “order of partials” rule, they must


be in the order as shown.
α
β
But this dislocation is now a planar object – it
can only exist in this form in the BCD plane.
D
The cross-slip plane is ADC.

αC
C

Steve Roberts – Microplasticity © S.G. Roberts 3:23

Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A
Splits into two partials:

DC ⇒ Dα + αC

Following the “order of partials” rule, they must


be in the order as shown.
α
β
But this dislocation is now a planar object – it
can only exist in this form in the BCD plane.
D
The cross-slip plane is ADC.
αC
DC To cross-slip, the partials must recombine to
C create a pure screw dislocation.

Steve Roberts – Microplasticity © S.G. Roberts 3:24

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Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A
Splits into two partials:

DC ⇒ Dα + αC

Following the “order of partials” rule, they must


be in the order as shown.
α
β
But this dislocation is now a planar object – it
can only exist in this form in the BCD plane.
D
The cross-slip plane is ADC.
αC
To cross-slip, the partials must recombine to
C create a pure screw dislocation.
Dα This can then glide on the ADC plane – and it
will immediately dissociate:

DC ⇒ Dβ + βC

Steve Roberts – Microplasticity © S.G. Roberts 3:25

Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A
Splits into two partials:

DC ⇒ Dα + αC

Following the “order of partials” rule, they must


be in the order as shown.
α
β
Dβ But this dislocation is now a planar object – it
can only exist in this form in the BCD plane.
D
The cross-slip plane is ADC.
αC
βC To cross-slip, the partials must recombine to
C create a pure screw dislocation.
Dα This can then glide on the ADC plane – and it
will immediately dissociate:

DC ⇒ Dβ + βC

Steve Roberts – Microplasticity © S.G. Roberts 3:26

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Cross-slip

B
A screw dislocation on plane BCD (“a” plane)
A
Splits into two partials:

DC ⇒ Dα + αC

Following the “order of partials” rule, they must


be in the order as shown.
Dβ α
αC
But this dislocation is now a planar object – it
can only exist in this form in the BCD plane.
D
βC
Dα The cross-slip plane is ADC.

To cross-slip, the partials must recombine to


C αC
create a pure screw dislocation.

This can then glide on the ADC plane – and it


will immediately dissociate:

DC ⇒ Dβ + βC

The cross-slip continues by sideways


propagation of the constricted nodes.

Steve Roberts – Microplasticity © S.G. Roberts 3:27

Cross-slip

B
To allow cross-slip to happen, this constriction
A of the dissociated dislocation must form.

The partials which mutually repel each other


must be brought together.

This requires a local stress.

αC
DC
C

Steve Roberts – Microplasticity © S.G. Roberts 3:28

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Cross-slip

B
To allow cross-slip to happen, this constriction
A of the dissociated dislocation must form.

The partials which mutually repel each other


must be brought together.

This requires a local stress.

This may happen if there is an obstacle to


glide, and possibly also a pile up.

D The stacking fault energy will assist the


constriction force.
αC
Materials with a high stacking fault energy will
C have narrow stacking faults that constrict
relatively easily. Easy cross-slip.

Materials with a low stacking fault energy will
have wide stacking faults that constrict with
difficulty. Cross-slip more difficult.

Steve Roberts – Microplasticity © S.G. Roberts 3:29

Cross-slip – so what ?
Ease of cross-slip (or the lack of it) has strong effects on many aspects of mechanical behaviour.

Monotonic loading

A: early stages of workhardening


B - glide band spreading
Stress

- formation of new dislocation sources


- by-passing precipitates
A
B: later stages of workhardening
- as (A) and
- bypassing of locks and dislocation tangles

Strain
Fatigue:

- irreversible slip in cyclic loading


- stability of “persistent slip band” structures

Steve Roberts – Microplasticity © S.G. Roberts 3:30

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“Frank” loops & dislocations


C
B CCP layers seen “edge on”, with a
A random arrangement of vacancies.
C
B
A (more vacancies than are in thermal
C
equilibrium)

C
B
A
C Redrawn showing just the vacancies.
B
A
C

C
B
A Vacancies can lower their energy by
C forming a disc-shaped planar cluster.
B
A
C

C C The adjacent planes collapse into the


B B
A vacancy sheet.
A
C
B
B
A
A An intrinsic stacking fault is formed,
C
C bounded by a pure edge dislocation
loop.

Steve Roberts – Microplasticity © S.G. Roberts 3:31

Frank loops & Thompson’s tetrahedron


Because the dislocation loop surrounds a stacking
fault, it must be a partial dislocation.

The Burgers vector is the same all way round the loop.

b The Burgers vector is normal to a {111} plane, and is


of length equal to one {111} interplanar spacing.

b {111} b
a
b= < 111 >
3
b

A B
This is represented on the Thomson tetrahedron by a
vector of type Dδ.
δ
a
Dδ = [111]
3
The faulted loop would be on the (111) - ABC – plane.
D

Steve Roberts – Microplasticity © S.G. Roberts 3:32

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Frank loops - removal


a
b= < 111 >
3 The Burgers vector of the dislocation bounding the
stacking fault does not lie on any {111} glide plane.
b {111} b
The dislocation is sessile.

The loop can only shrink or grow by removal or addition


of vacancies – i.e. by climb.

Another way the stacking fault can be removed is by a


D
dislocation reaction.

The boundary dislocation has Burgers vector (say) δD.

C If this combines with a Shockley partial dislocation of


Burgers vector (say) Aδ, a perfect dislocation is formed.
δ
δD + Aδ ⇒ AD
A B

Steve Roberts – Microplasticity © S.G. Roberts 3:33

Frank loops - conversion


D
Frank loop, b= δD, with stacking fault.

δ
A B

δD

δD
δD

δD

Steve Roberts – Microplasticity © S.G. Roberts 3:34

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Frank loops - conversion


D
Frank loop, b= δD, with stacking fault.

Shockley partial loop, b= Aδ, nucleates


C within the Frank loop;
δ
A The Shockley partial can glide in the plane
B
of the loop.

δD

Aδ δD
AD

δD

Steve Roberts – Microplasticity © S.G. Roberts 3:35

Frank loops - conversion


D
Frank loop, b= δD, with stacking fault.

Shockley partial loop, b= Aδ, nucleates


C within the Frank loop;
δ
A The Shockley partial can glide in the plane
B
of the loop.

The Shockley partial traverses the Frank


AD loop

Aδ δD
AD

AD

Steve Roberts – Microplasticity © S.G. Roberts 3:36

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Frank loops - conversion


D
Frank loop, b= δD, with stacking fault.

Shockley partial loop, b= Aδ, nucleates


C within the Frank loop;
δ
A The Shockley partial can glide in the plane
B
of the loop.

The Shockley partial traverses the Frank


AD loop, and completely coneverts it to a
perfect dislocation loop, b= AD.

Note that the perfect lattice dislocation can


AD AD glide – but only in the ADC or ADB planes.

It cannot glide in its own loop plane.


AD
This is called a prismatic dislocation loop.

Steve Roberts – Microplasticity © S.G. Roberts 3:37

Dislocations in hexagonal close-packed metals


c/a ratio of ideal structure = √(8/3) = 1.633

Metals with c/a ≥ 1.6333 Metals with c/a < 1.6333

Basal slip is favoured. Prism plane slip is favoured.


Slip systems are (0001)<1120> Slip systems are {1100}<1120>

Metal c/a CRSS on Metal c/a CRSS on CRSS on


(0001)<1120> (0001)<1120> {1100}<1120>

Zn 1.856 0.18 MPa Ti 1.587 110 MPa 49 MPa


Mg 1.624 0.43 MPa Zr 1.593 ? 6 MPa
Cd 1.886 0.57 MPa
Can also get slip on {1101}<1120>

(1010)
(0001) (1101)

[1210] [1210] [1210]

[2110] [1120] [2110] [1120] [2110] [1120]

Steve Roberts – Microplasticity © S.G. Roberts 3:38

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Basal slip in hcp metals

Basal slip is very similar to {111}<110> slip


in ccp metals. Action of a single partial dislocation produces
a stacking fault.
The Burgers vector is that of closest atomic
spacing in the close-packed plane. The stacking fault locally has a three-fold
layer repeat – a few layers of ccp structure.
Perfect dislocations will split into partial
dislocations.

a a a
[11 2 0] ⇒ [10 1 0] + [01 1 0]
3 3 3
Steve Roberts – Microplasticity © S.G. Roberts 3:39

Non-basal-plane slip in hcp metals

(1010) There is no possible “stacking fault” arrangement on


these crystal planes.

[1210] However, a low energy fault is possible on the basal


plane.
[2110] [1120]
Even though dislocations glide on the prism or pyramidal
plane, the relaxed core structure is extended on the basal
plane.

The dislocations have non-planar cores, which must re-


arrange before glide can happen.

(1101) This is why non-basal glide requires a high critical


resolved shear stress.
[1210]

[2110] [1120]

Steve Roberts – Microplasticity © S.G. Roberts 3:40

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Dislocations in body-centred cubic metals


[001]
BCC metals include:

Fe, Mo, W, Ta, V, Cr, Nb, Na, K

a
Slip always has Burgers vector b = 111
2
Possible slip planes are {110}, {112}, {123}.

Any given Burgers vector lies in:


[100] 3 {110} planes
3 {112} planes
6 {123} planes
(101)
a
b= [111] There is no low-energy stacking fault structure
2
on any of these planes.

Dislocations do not dissociate.


[010]

Steve Roberts – Microplasticity © S.G. Roberts 3:41

Screw dislocations in bcc metals – cross slip

Cross-slip of screw dislocations is very easy: This ready cross-slip means that screw
dislocations will follow the easiest path through a
- there are no possible stacking faults, so the bcc crystal, changing frequently between slip
screw dislocations are not dissociated; lanes to avoid obstacles.

- there are very many possible slip planes for a On the “optical microscope” scale, this appears
given dislocation. as “wavy slip”.

Video shows cross-slip of screw dislocations in Mo

Steve Roberts – Microplasticity © S.G. Roberts 3:42

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Screw dislocations in bcc metals – core structure


(011)
[211]
Screw dislocations in bcc metals have
[121] non-planar cores.

Illustrations show atomistic simulations


(101) [112] of two possible core structures.

The whole dislocation has b = ½ a [111]


(111) (normal to plane of the page)
plane
Arrows at each atom position indicate
displacement from that position when
(110) screw dislocation is present at the
centre.

The shifts are concentrated equally


along three of the potential slip
directions.

This is not dissociation – there are no


well separated dislocations bounding
stacking faults. The core is just
“delocalised”.

Steve Roberts – Microplasticity © S.G. Roberts 3:43

Screw dislocations in bcc metals – glide


The screw dislocation core is spread over three
τ potential glide planes.

If a shear stress is applied, before the dislocation can


glide, it has to re-arrange itself to be nearly planar
before glide can occur.

Pictures show atomistic simulations of changes in


core structure under stress.

Results:
τ
• Glide of screw dislocations is difficult.

τ • Thermal activation will assist core re-arrangements


and hence critical resolved shear stress for glide.

• Schmid’s law is not obeyed as:

• Glide in one sense is easier than glide in the


other (the “tension-compression asymmetry”)

• Non-shear stresses can affect core re-


arrangements and hence glide stress.
τ

Steve Roberts – Microplasticity © S.G. Roberts 3:44

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Dislocation loops in bcc metals


Edge dislocations in bcc metals have undissociated
but planar cores.

They can move much more readily than screw


dislocations.

Consequences:

Dislocation loops tend to have long, straight, slow


moving screw segments and short, rapidly moving
edge segments.

Operation of dislocation sources is be restricted by


the rate at which screw dislocations can “get out of
the way”.

Videos:

Upper: Molybdenum - movement of fast edge dislocation


trailing long screw dislocation;
Lower: Molybdenum - operation of “half-Frank-Read”
dislocation source

Courtesy of I. Robertson et al., University of Illinois at Urbana-Champaign

Steve Roberts – Microplasticity © S.G. Roberts 3:45

Dislocations in bcc metals - general


CRSS (MPa)
30
Dislocation mobility in bcc metals varies
0.01% C Iron strongly with impurity content:

20 - even a few ppm of interstitial impurities


0.001% C give “Cottrell atmospheres”.

10 "pure"
- stress fields around interstitial solutes in
bcc have strong shear as well as
0
dilatational components – interact
0 50 100 150 200 250 300 strongly with both edge and screw
Temperature (K)
dislocations.

Dislocation mobility in bcc metals varies - thermal activation is needed to pull


strongly with temperature (especially at dislocation cores off these solutes.
low temperatures):

- “fairly directional” bonding means


moderate activation energy for glide even
of edge dislocations

- thermal activation is needed to put


screw dislocations into glide
configuration

Steve Roberts – Microplasticity © S.G. Roberts 3:46

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Intermetallic compounds: structures


[001]
[001] “L12” structure. “L10” structure.

Cu3Au, Ni3Al, etc. TiAl

[100] [010]
[100] [010]

There are very many more crystal


“B2” structure. structures of a huge variety of intermetallic
materials.
CuZn
Some are closely related to the simple
structures exhibited by elemental metals
(“superlattices”).

Others are very complex….

Steve Roberts – Microplasticity © S.G. Roberts 3:47

Ordered intermetallics: superlattice dislocations

The slip planes in the L12 structure (e.g. Ni3Al)


are {111} – just like in ccp metals.
Al
But the lattice is now simple cubic – the
Ni
shortest lattice vector in this plane is a<110>.

The “normal” a/2 <110> vector moves an (e.g.)


Al atom on the site of a (e.g.) Ni atom.

These a/2 <110> dislocations can also split


into a/6 <211> partial dislocations.

Steve Roberts – Microplasticity © S.G. Roberts 3:48

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Dislocation structure in L12 intermetallics


Anti-phase
Stacking fault boundary Stacking fault

Al

Ni

The line energy = Gb2/2


criterion favours splitting
of the lattice dislocation A complicated structure results – the partials repel each
into the four a/6 <211) other elastically but are held together by the energies of
partials. the resulting stacking faults.

The central fault, where Al is “swapped” onto on Ni site,


is called an “Anti-phase boundary” (APB).

Steve Roberts – Microplasticity © S.G. Roberts 3:49

APB energies and the “yield stress anomaly”

In some L12 materials, notably Ni3Al,


the APB has a lower energy on the
{100} planes than on the {111} planes.

Anti-phase So, given some thermal activation to


boundary on (111) “pinch” the leading stacking fault,

Steve Roberts – Microplasticity © S.G. Roberts 3:50

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APB energies and the “yield stress anomaly”

In some L12 materials, notably Ni3Al,


the APB has a lower energy on the
{100} planes than on the {111} planes.

Anti-phase So, given some thermal activation to


boundary on (111) “pinch” the leading stacking fault,

Steve Roberts – Microplasticity © S.G. Roberts 3:51

APB energies and the “yield stress anomaly”

Anti-phase In some L12 materials, notably Ni3Al,


boundary on (100) the APB has a lower energy on the
{100} planes than on the {111} planes.

Anti-phase So, given some thermal activation to


boundary on (111) “pinch” the leading stacking fault,
a screw dislocation can cross slip
onto a {100} plane.

Steve Roberts – Microplasticity © S.G. Roberts 3:52

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APB energies and the “yield stress anomaly”

Anti-phase In some L12 materials, notably Ni3Al,


boundary on (100) the APB has a lower energy on the
{100} planes than on the {111} planes.

So, given some thermal activation to


“pinch” the leading stacking fault,
a screw dislocation can cross slip
onto a {100} plane.

Steve Roberts – Microplasticity © S.G. Roberts 3:53

APB energies and the “yield stress anomaly”

Anti-phase In some L12 materials, notably Ni3Al,


boundary on (100) the APB has a lower energy on the
{100} planes than on the {111} planes.

So, given some thermal activation to


Stacking fault “pinch” the leading stacking fault,
on (111) a screw dislocation can cross slip
onto a {100} plane.

It will finally end up as shown –

Two screw dislocations dissociated on


the glide plane, but connected by an
low-energy APB on a non-glide plane.

This dislocation can only move by re-


cross-slipping to the higher-energy
planar glide configuration.

Steve Roberts – Microplasticity © S.G. Roberts 3:54

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APB energies and the “yield stress anomaly”

In some L12 materials, notably Ni3Al,


the APB has a lower energy on the
{100} planes than on the {111} planes.

So, given some thermal activation to


“pinch” the leading stacking fault,
a screw dislocation can cross slip
onto a {100} plane.

It will finally end up as shown –

Two screw dislocations dissociated on


the glide plane, but connected by an
low-energy APB on a non-glide plane.

This dislocation can only move by re-


cross-slipping to the higher-energy
planar glide configuration.
“Locked” dislocation with kinks At higher temperatures, more
segments of dislocations transfer to
the non-glide arrangement.

The Yield stress rises.

Steve Roberts – Microplasticity © S.G. Roberts 3:55

Dislocations in ionic crystals

Bonding is non-directional,

Shear displacements of atoms when


dislocation cores move is easy –

except that strong fluctuations of


energy will occur as ions of like or
opposite charge move closer to each
other.

These energy fluctuations will


determine flow stresses and even
slip systems.

O2-, Cl-, F- …

Mg2+, Na+, Li+, …

Steve Roberts – Microplasticity © S.G. Roberts 3:56

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Dislocations in ionic crystals

In the “rock-salt” structure,

{111} planes contain ions all of the


same charge.

Dislocations gliding on {111} would


have very strong charge interactions.

Slip on {111} isn’t observed – other


systems are much easier to operate.

O2-, Cl-, F- …

Mg2+, Na+, Li+, …

Steve Roberts – Microplasticity © S.G. Roberts 3:57

Dislocations in ionic crystals

In the “rock-salt” structure,

{110} planes are charge-neutral, and


contain the shortest lattice vector.
a
b= 110
2
Motion of dislocations with this
Burgers vector do not bring like
charges too close together.

Slip on this system is fairly easy.

O2-, Cl-, F- …

Mg2+, Na+, Li+, …

Steve Roberts – Microplasticity © S.G. Roberts 3:58

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Dislocations in ionic crystals

(100)

In the “rock-salt” structure,

{110} planes are charge-neutral, and


contain the shortest lattice vector.
a
b= 110
2
Motion of dislocations with this
Burgers vector do not bring like
[011]
charges too close together.
[011]
Slip on this system is fairly easy.

Edge dislocation in rock-salt structure,


on {110}<110> slip system.

(alternate layers have atoms in same


positions, but with opposite charges)

Steve Roberts – Microplasticity © S.G. Roberts 3:59

Dislocations in ionic crystals

In the “rock-salt” structure,

{100} planes are charge-neutral, and


contain the shortest lattice vector.

a
b= 110
2
Motion of dislocations with this
Burgers vector do not bring like
charges very close together, but
planes are more closely spaced than
{110} planes. Charge interactions
are stronger than for {110} slip.

Slip on this system is possible, only


at high stresses. O2-, Cl-, F- …

Mg2+, Na+, Li+, …

Steve Roberts – Microplasticity © S.G. Roberts 3:60

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Dislocations in ionic crystals

C.R.S.S. (MPa)
MgO is typical of a wide variety of ionic
500 materials:

- Slip systems determined by strength of


400 ionic effects on dislocation motion as
much as by “straight” crystallography.
<110>{001}
300
- Ionic repulsion as dislocation moves
makes even “easy” slip systems difficult
200 to operate
- thermal activation can make slip
easier
100
- Limited number of active slip systems at
<110>{110} low temperatures
0 - may not meet Von Mises’ criterion
0 500 1000 1500 - Charged impurities (e.g. Fe3+, Cr3+) have
Temperature (K) very large effects on flow stress even at
ppm levels.

Steve Roberts – Microplasticity © S.G. Roberts 3:61

Dislocations in covalent crystals

Covalent bonds have well-defined


lengths and interbond angles:

For materials with the FCC “diamond


cubic” structure:

C: 0.154 nm, 109.4º


Si: 0.235 nm, 109.4º
Ge: 0.245 nm, 109.4º
SiC: 0.307 nm, 109.4º
GaAs: : 0.400 nm, 109.4º

Steve Roberts – Microplasticity © S.G. Roberts 3:62

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Dislocations in covalent crystals

Covalent bonds have well-defined


lengths and interbond angles.

For materials with the FCC “diamond


cubic” structure:

C: 0.154 nm, 109.4º


Si: 0.235 nm, 109.4º
Ge: 0.245 nm, 109.4º
SiC: 0.307 nm, 109.4º
GaAs: : 0.400 nm, 109.4º

As in the cubic close-packed metals,

Glide planes: {111}


Burgers vectors: a/2 <110>

(can still use Thompson’s tetrahedron)

But these are not close-packed planes or


directions.

Steve Roberts – Microplasticity © S.G. Roberts 3:63

“Peierls valleys” and dislocation types in diamond structure

Dislocation cores are highly structured:

Core energy depends strongly on direction.

Dislocations lie along <110>.

[ Electron Beam Induced Conductivity


(EBIC) image in SEM. Demonstrates
dislocations are electrically active.
Important in semiconductor devices.]
P.R. Wilshaw 1989

60º 60º
screw
Dislocations thus are likely to be either pure
screw or “ 60º ” type.

What will their core structure be ?

60º screw 60º

Steve Roberts – Microplasticity © S.G. Roberts 3:64

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“Peierls valleys” and dislocation types in diamond structure

As in ccp metals, dislocations in diamond


60º 60º structure are always dissociated – e.g.:
screw
a a a
<110> [1 1 0](111) ⇒ [2 1 1](111) + [1 2 1](111)
2 6 6
Dissociation width depends on shear
60º screw 60º modulus G and stacking fault energy γ in
the usual way.

The (a/6)<211> partial Burgers vectors


30º are at 30º to the perfect (a/2)<110>
vector.
90º
Dissociation thus produces two types of
dislocation:

“30º” – Burgers vector at 30º to line


“90º” – pure edge.

So what structure do these have ?

Steve Roberts – Microplasticity © S.G. Roberts 3:65

Dislocation core structure in diamond structure

Looking down the line direction of a dissociated


60º dislocation.

Stacking fault is visible as two sets of “ABA”


bonds.

FCC structural unit

Stacking fault
structural unit

High Resolution Electron Microscopy (HREM)


image of this type of stacking fault.

Steve Roberts – Microplasticity © S.G. Roberts 3:66

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The Dislocation in Literature

Only infinite jumble and mess and dislocation, Finest dislocations of the avant-garde
Backed by a solemn appeal, 'For God's sake, do not stir, there!' turn out to be the simplest captions of
Arthur Hugh Clough, The Bothie of Tober-na-vuolich: a Long-vacation
Pastoral.
disease….
Peter Porter, The Worst Inn's Worst Room (1994)

In Pope, there are no disharmonies and


dislocations ever and anon to grate and interrupt;
all in him is perfect…. Dislocation, perhaps!" muttered the Doctor:
James Stirling, Burns in drama (1878) "let us hope there is no worse injury done.”
Charlotte Brontë, Villette (1853)

"Any dislocation, and we are thrown out again!


We must hold together if this riddle is ever to be read.” Every half step he attempted was like a dislocation.
George Meredith, The Egoist (1879)
His groans and grunts were frightful.
George Meredith, The Ordeal of Richard Feverel (1859)

Thomson … went up to assist Mr. Morgan in the reduction of the dislocation.


--- When this was successfully performed, they wished me joy…
Tobias Smollett, Roderick Random (1748)

One of the terrible dislocations of our habits of mind.


Joseph Sheridan Le Fanu, Uncle Silas (1864).

Steve Roberts – Microplasticity © S.G. Roberts 3:67

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Why do materials have any strength ?


Calculations show that it should only need a few Nm-2 to move dislocations
about in metals - and experiments on pure metals show that this is the case.

Strength ≡ restricted dislocation motion.

• Effects of bonding type on ease of dislocation motion.


¾ choice of basic material
• Grain boundaries as blocks to dislocation motion
¾ “grain refinement” hardening (and toughening)
• Internal stress fields from dissolved atoms interact with dislocation stress fields
¾ “solute hardening”
• Internal stress fields from precipitates interact with dislocation stress fields
¾ “precipation hardening” (“age hardening”)
• Precipitates with “hard” crystal structures act as local blocks to dislocations
¾ “precipation hardening” (“age hardening”)
• Immobile dislocations block mobile dislocations
¾ “work hardening”
• Use phase chages in basic material to produce fine, strained microstructures
¾ “quenching”
Microplasticity 5 – Strengthening S.G. Roberts 5: 1

Effects of bonding type on yield strength

Yield Strength - resistance to slip by


dislocation motion increases as the
directionality and rigidity of interatomic
bonding increases.

Increasing directionality of bonding: increasing yield stress and hardness

Close-packed Other metals Ionic Intermetallic Covalent


metals compounds compounds solids

copper, iron, NaCl, MgO CuAl2, diamond,


e.g.: aluminium tungsten TiAl, Ni3Al SiC, Al2O3

Nearly non- Some Bonding by Ordered structures “Ceramics”: Very


directional directionality in electrostatic with fairly directional strongly directional
bonding. bonding. attraction: not bonding. bonding.
directional but slip
Dislocation Dislocation moves strongly Dislocation motion Dislocation motion
motion easy motion fairly charged ions past difficult. very difficult.
easy (varies each other.
with Can use as fine Can use in
temperature) Dislocation motion dispersions to composites
fairly difficult harden metallic
alloys
Microplasticity 5 – Strengthening S.G. Roberts 5: 2

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Effects of Bonding type – “Isomechanical Groups”

Hardness (MPa) Hardness / Young’s Modulus

104 Si 10-1
Ge

Si
103 Ge
W
10-2

Fe Mo
102
Pb Al
Cu Pb
Al
10 10-3 W
Mo
Fe Cu
0 400 800 1200 1600 2000 0 0.2 0.4 0.6 0.8
Temperature (K) T / Tmelt

Microplasticity 5 – Strengthening S.G. Roberts 5: 3

Hardening by substitutional solutes


Possible interactions between Dislocations and Solutes

• Elastic
– Stress field of dislocation interacts with stress field around solute
• Modulus
– Dislocation energy varies where solute locally changes bond stiffness
• Stacking fault
– Stacking fault energy varies if solute present
• Electrical
– Dislocations with charged cores (ionic materials) will have strong interactions with
charged point defects
• Short-range order & Long-range order
– Motion of dislocation / stacking fault will change local ordering, hence energy.

In all cases, any interaction between dislocation and solute will harden the material:
- attractive ⇒ dislocations “pinned” near solute atoms
- repulsive ⇒ dislocations have to be “pushed past” solute atoms

Microplasticity 5 – Strengthening S.G. Roberts 5: 4

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Solution hardening

Interaction energies between


stress fields of the moving
Energy dislocation and the static
misfitting solute atoms give rise
to widely varying dislocation
enrgy with position.

Since

Dislocation dE
F=
Position dx

This implies a high stress to


move dislocations through
such an array of obstacles.

[Any array of small regions with


associated stress fields will
give similar effects]

Microplasticity 5 – Strengthening S.G. Roberts 5: 5

Substitutional solid solution hardening in 3D

Case shown is for solute atoms


smaller than the “parent” atoms.

Solutes below the dislocation’s slip plane


C
Solutes above the dislocation’s slip plane
T (N.B. – only one sort of solute atom –
colour is just to indicate position.)

Minimum energy
configurations of dislocations
2 are a compromise between
“line tension” (energy /
length) and attraction to /
1 repulsion from solute atoms.

Microplasticity 5 – Strengthening S.G. Roberts 5: 6

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Strong “diffuse” obstacles –


interacting via long range stresses

Mean stress on dislocations (the “internal stress”) = τi

Gb
τi =
2R
Gb
R=
2τ i
If R< λ, the dislocation line can bend tightly enough for it
to find a minimum energy shape through the array of
λ stress centres.

“Strong Interactions” control the shape of the dislocation


Dislocation line tends to bypass line.
obstacles one at a time.
Flow stress is that to overcome the mean internal stress

2
τ flow = τi
π

Microplasticity 5 – Strengthening S.G. Roberts 5: 7

Weak “diffuse” obstacles –


interacting via long range stresses

Mean stress on dislocations (the “internal stress”) = τi


Gb
R=
2τ i
If R > λ, the dislocation line can’t bend tightly enough for it
to “weave” between the obstacles.

Line Tension is a strong influence on the shape of the


dislocation line.

L λ Moving segments of the dislocation line are much longer


(L) than the obstacle spacing λ.

Number of obstacles in length L, n:

L
n=
λ

In a random arrangement, there will be an excess of


obstacles of one “sense” over the other = √n

Microplasticity 5 – Strengthening S.G. Roberts 5: 8

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Weak “diffuse” obstacles –


interacting via long range stresses
Mean stress on dislocations
(the “internal stress”) = τi
Over length L, we have √n active obstacles,
each acting over length λ
2
τ flow bL = n λτib
π
1
2  λ 2
τ flow = τi  
π L
Estimate L by assuming advance distance = l,
dislocation line curvature controlled by applied stress:

λ λ
L = R − R 2 − (L / 2)2
2
L2 L2 τ flow
λ≈ =
4R 2Gb
R This gives:
λ
1
2  τi λ  3
τ flow = 
4 
 τi
π 3  Gb 
L

Microplasticity 5 – Strengthening S.G. Roberts 5: 9

Weak “diffuse” obstacles –


interacting via long range stresses

0.50 50

0.40 40
λ = 10nm
G = 40 GPa
τ flow 0.30 30
L b = 0.3 nm

τi 0.20 20 λ

0.10 10

0 0
0 100 200 300 400 500
τi (MPa )

1
2  τi λ  3 For typical values of λ, G, b, τi,
τ flow = 
4 
 τi
π 3  Gb  τflow ~ 0.1 - 0.3 τi

Microplasticity 5 – Strengthening S.G. Roberts 5: 10

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Solute – Dislocation Elastic Interactions: the maths

σ from dislocation
⇒ hydrostatic stress σH

rM

rF
rS
y

r
rM = size of matrix atom (≡ size of “hole”)
θ
rS = size of solute atom
x
rF = final size
⇒ hydrostatic misfit stress & strain

Microplasticity 5 – Strengthening S.G. Roberts 5: 11

Solute – Dislocation Elastic Interactions: the maths

Model: solute atom is elastic sphere of same E, G, ν as matrix.


Radius before insertion = rS = (1 + δ) rM.
rM
Radius after insertion = rF = (1 + ε) rM.
rF
rS

(1 + ν )
ε= δ
Vmis = VS − VM 3(1 − ν )
(1 + ν )
= 4πrM2 (δrM ) ∆V = 4πrM3 δ
3(1 − ν )
= 4πrM3 δ (1 + ν )
= Vmis
∆V = VF − VM 3(1 − ν )
= 4πrM3 ε

( Proof of this is an “exercise for the student”)

Microplasticity 5 – Strengthening S.G. Roberts 5: 12

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Solute – Dislocation Elastic Interactions: the maths


Interaction Energy, Ei = P.∆V

(1 + ν ) 2(1 + ν ) Gb y
Ei = 4πrM3 δ
y 3(1 − ν ) 3 2π(1 − ν ) x + y 2
2

P
However, this is for an infinite matrix:
r for a finite matrix, there is a correction factor
of : 3(1 − ν )
θ
(1 + ν )
x
-effectively ∆V = VH, = 4πra2 δ, and so
2(1 + ν ) Gb y
Hydrostatic Stress from disln, P: Ei = 4πrM3 δ
3 2π(1 − ν ) x 2 + y 2
P = − 31 (σ xx + σ yy + σ zz ) 4Gb rM3 δ (1 + ν ) sin θ
=
2(1 + ν ) Gb y 3 (1 − ν ) r
=
3 2π(1 − ν ) x + y 2
2

Microplasticity 5 – Strengthening S.G. Roberts 5: 13

Solute – Dislocation Elastic Interactions: the maths

The glide force on the dislocation is:

d
Fx = Ei
dx
y
4Gb rM3 δ (1 + ν ) d  y 
P =  
3 (1 − ν ) dx  x 2 + y 2 
r
8Gb rM3 δ (1 + ν ) xy
=
θ 3 (
(1 − ν ) x 2 + y 2 )2

x 8Gb rM3 δ (1 + ν ) sin θ cos θ


=
3 (1 − ν ) r2
4Gb rM3 δ (1 + ν ) sin θ
Ei = The maximum glide force is at θ = 60°:
3 (1 − ν ) r
4Gb rM3 δ (1 + ν ) y MAX 2Gb rM3 δ (1 + ν ) 1
= Fx =
3 (1 − ν ) x 2 + y 2 3 (1 − ν ) r
2

( Proof of this is an “exercise for the student”)

Microplasticity 5 – Strengthening S.G. Roberts 5: 14

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Solute – Dislocation Elastic Interactions: the maths

y The maximum interaction energy


P is when r = b and θ = 90°:
MAX 4G rM3 δ (1 + ν )
r Ei =
3 (1 − ν )
θ = 60°
≈ G ΩM δ
x
These rough theoretical values
MAX 2Gb rM3 δ (1 + ν ) 1 are an overestimate, but are within
Fx =
3 (1 − ν ) r
2
an order of magnitude of real
values.
The absolute maximum glide force
exerted by the misfitting solute on the
Typical values:
dislocation is when r = b and θ = 60°:
MAX 2G rM3 δ (1 + ν ) EiMAX = 3 δ eV for C.P. metals
Fx = EiMAX = 20 δ eV for covalent solids
3 b (1 − ν )
GΩM δ

b
Microplasticity 5 – Strengthening S.G. Roberts 5: 15

Strength of solution hardening


Flow Stress Flow Stress
(MPa) (MPa)
6

30
4
20
2
10

0 0
Ag Au Al 1 2 3 %Cu

r = 0.2889 nm r = 0.2884 nm r = 0.2863 nm r = 0.2556 nm

misfit, δ = ~ 0.17 % misfit , δ = ~ 8 %

Strength of hardening effect is (to a good approx.) proportional to:


MAX
Ei ≈ G ΩM δ 1. amount of solute
2. solute misfit, δ
MAX
Fx ≈ G ΩM δ b 3. elastic modulus of matrix

Effects of multiple solutes are roughly additive.

Atomic size data: www.webelements.com

Microplasticity 5 – Strengthening S.G. Roberts 5: 16

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Solution hardening – interstitial solutes

A limited number of cases, The atoms here are shown smaller than they
but of great importance: actually are relative to the b.c.c. unit cell.

C, N in Iron (body centred cubic) The A-A spacing is smaller than the B-B spacing,
(and other b.c.c. metals) and determines the size of interstitial atom that
will “fit”.
O in Titanium (close packed hexagonal)
rint.
< 0.29
A rhost
c B Actual radius ratios:
B
rnitrogen rcarbon
= 0.44 = 0.46
I riron riron
B B
Result: each interstitial atom has a large and
A non-spherically symmetric stress field around it:
b
Shears as well as dilatations.

a Misfit , δ = ~ 10 % to 100%

Microplasticity 5 – Strengthening S.G. Roberts 5: 17

Interstitial solutes – dislocation “pinning”

Three features of interstitial solutes in bcc metals make them


powerful hardening agents:

•They have very large stress fields around them


• so they can lower energy by “sitting” at dislocation cores
•The stress fields have both shear and dilatational components
• so they pin both edge and screw dislocations
•They can diffuse rapidly, even at room temperature
• so they can “find” the dislocations in hours or days.

High Stress
applied

Dislocation pinned Dislocation unpinned and


Solute diffusion to mobile at lower stress
static dislocation

Microplasticity 5 – Strengthening S.G. Roberts 5: 18

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Interstitial solutes and dislocations: the maths

y
r  − EMAX 
c core = c bulk exp i

θ  kT 
x

Elastic Interaction Energy:

4Gb rM3 δ (1 + ν ) sin θ Take cbulk = 0.1 at%


Ei =
3 (1 − ν ) r
100%
MAX
Ei ≈ G ΩM δ Ei = 0.2eV
80% 0.3eV
(theoretical value – overestimate) 0.4eV
60%
0.5eV
For interstitial solutes, ccore
40%

Misfit , δ = ~ 10 % to 100% 20%

(substnl. solutes: 0% to ~14%) 0


0 200 400 600 800 1000

Temperature (K)
Typical binding energy = 0.2 to 0.5 eV

Microplasticity 5 – Strengthening S.G. Roberts 5: 19

Yield point and strain ageing


Stress (MPa)

Upper Yield
500hr Stress
4hr
300 0.5hr
Lower Yield
Stress
U.Y.S.

200

Ageing
unload –
L.Y.S. age -
reload

100 0.03%C steel, 60ºC

0 5 10
Strain (%)

Microplasticity 5 – Strengthening S.G. Roberts 5: 20

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Solute – stacking fault interactions


Hardening if solute atoms have different solubility in stacking fault
than in matrix.

With solute atoms with higher solubility in stacking fault:


A c0
A: (Non equilibrium)
Dislocations and stacking fault.
c0 Solute atoms at concentration c0 throughout

B: (Equilibrium)
Solute atoms at concentration c0 in bulk,
c1 ( > c0) in stacking fault.
B Stacking fault energy per unit area is lowered.
Stacking fault widens;
c1 Dislocation stacking fault energy per unit length ⇑
Dislocation elastic energy per unit length ⇓
c0 Overall dislocation energy ⇓

To move dislocation, must leave solute cloud behind + go


back to higher energy configuration B.
“Suzuki effect”
Similar (though weaker) effects to “Cottrell atmospheres”

Microplasticity 5 – Strengthening S.G. Roberts 5: 21

Solutes – modulus interactions

• Point defects can change the local elastic modulus of the material
– defect - matrix bonds may be “softer” or “harder” than those of pure matrix
– visible as a macroscopic change in modulus
– regions close to solute will have large change in modulus
– dislocation stress field energy locally changed
– ∴ elastic interaction between dislocation and point defect

• Soft defects (e.g. vacancy) (modulus locally decreased)


– attractive interaction with dislocations

• Hard defects (modulus locally increased)


– repulsive interaction with dislocations

[ Compare with “image forces” ]

Microplasticity 5 – Strengthening S.G. Roberts 5: 22

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Modulus interactions – the maths


Elastic energy δE of any Simplest case is for screw dislocations,
small volume element δV with shear modulus locally changed at a
radius r from G to G`:
δE = 1
(∑ σ ε )δV
∑ (σ′ − σ )ε
2 ij ij
ij ij ij = ( τ′ − τ)γ
Assume that the strain field around (G′ − G)b b
the dislocation stays the same, but =
that the local stress changes in 2πr 2πr
response to modulus changes.
Change in energy of this volume
element::
Gb 2 rs3
∆(δE) = 1
2
(∑ (σ′ − σ )ε )δV
ij ij ij
So that: ∆E = ηG
6π r 2
Assume single solute atom,
changing modulus over radius rs: G′ − G
where ηG =
G
∆E = 1
2
(∑ (σ′ − σ )ε )
ij ij
4
ij 3 πrs3

Microplasticity 5 – Strengthening S.G. Roberts 5: 23

Modulus interactions – the maths


d∆E
Fx = −
y
rs dx
Gb 2 x rs3
= ηG
r
3 π ( x 2 + y 2 )2
θ
Gb 2 rs3
= ηG cos θ
x
3π r 3
Interaction energy between
Gb 2
dislocation and modulus-changed FxMAX = ηG when r = rs and θ = 0
region around solute atom: 3π
These effects, for both screw and edge
Gb 2 rs3 dislocations, are generally weaker than
∆E = ηG elastic interactions.
6π r 2
∆E decays as 1/r2
Gb 2 rs3
= ηG (for elastic interactions decays as 1/r).
6π ( x 2 + y 2 )
Can be important for chemically different
solute atoms with small size mismatches.

Microplasticity 5 – Strengthening S.G. Roberts 5: 24

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Electrical solute – dislocation interactions

(100) Non isovalent impurities create charged point defects:

e.g. Cr3+ in Mg2+O2-

Mg O Mg O Mg O

O Cr O - O Mg
+ -

[011] Mg O Mg O Cr O
+
[011]
O Mg O Mg O Mg
Edge dislocation in rock-salt structure,
e.g. MgO: {110}<110> slip system. For every two Cr3+ there must be one Mg2+ vacancy.

(alternate layers have atoms in same These charged defects interact very strongly with the
positions, but with opposite charges) kinks on the dislocations:

JOGS have a non-cancelled charge. A few 100’s of ppm charged impurity can double the
hardness of MgO

Microplasticity 5 – Strengthening S.G. Roberts 5: 25

Hardening by precipitates
1. Coherency strains
• Long range stress fields around coherent precipitates
2. Semi-coherent precipitates
• Long and short-range interactions with interfacial dislocations
3. Interfacial energy and morphology
• “Cutting” of precipitates increases their surface area
4. Lattice friction stress
• Precipitates have higher (or lower) σy than matrix
5. Stacking fault energy
• Dissociated dislocations have different SFE in precipitates
6. Ordered precipitates
• Burgers vector multiplies and dissociation become more complex in
precipitates
7. Modulus effects
• Dislocations have different line energy in precipitates
8. Bowing round precipitates. (“Orowan mechanism”)
• Dislocation curvature increases on bypassing precipitates

Long range interactions “Cutting” interactions “By pass” interaction

Microplasticity 5 – Strengthening S.G. Roberts 5: 26

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Hardening by precipitates
Hardening by strain fields

Strain fields
around Guinier-
Preston zones
of copper in
aluminium

Small precipitates may be "coherent" with the matrix.

All lattice planes, including slip planes are continuous


as they pass through the precipitates; the change in
lattice parameters in the precipitate causes each one to
be surrounded by a (relatively long range) stress field.

This interacts with the stress field of dislocations.

∆τ ~ 2 G ε f
ε = misfit strain, f = volume fraction of ppts

Microplasticity 5 – Strengthening S.G. Roberts 5: 27

Hardening by precipitates
Hardening by interaction with interfacial dislocations

Semi-
coherent

S` phase
in Cu–A -Mg
θ` precipitates in Al - Cu

2 µm

Medium-sized precipitates, if too big to be fully coherent


may be “partially coherent" with the matrix.
Incoherent
Most lattice planes, including slip planes are continuous
S phase
as they pass through the precipitates; mistfit strain is
Al2CuMg
taken up by interfacial dislocations.

Stresses from these interact with the stress field of the


mobile dislocations.
Charai et al., Acta mater. 48 (2000) 2751

Microplasticity 5 – Strengthening S.G. Roberts 5: 28

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Hardening by precipitates
Hardening by interaction with interfacial dislocations

σxy

(generated using the dislnwall.xls spreadsheet)

Microplasticity 5 – Strengthening S.G. Roberts 5: 29

Dislocations and weak obstacles

Precipitates on
dislocation’s
slip plane

Dislocation line

Microplasticity 5 – Strengthening S.G. Roberts 5: 30

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Dislocations and weak obstacles

Microplasticity 5 – Strengthening S.G. Roberts 5: 31

Dislocations and weak obstacles

Dislocations can cut through the precipitates (and their stress fields):
but the bigger and more “compound-like” they are, the more difficult
this is.

Note that the precipitates get “chopped up” with increasing strain.

Microplasticity 5 – Strengthening S.G. Roberts 5: 32

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Interfacial energy and morphology

coherent or
semi-coherent ppt
γ

Surface energy = 4πr2γ

Ag G.P. zones in Cu Surface energy ≅ (4πr2 + πrb )γ

dE ∆E 1
Fobst = ≅ = πrγ
dx 2b 2

Microplasticity 5 – Strengthening S.G. Roberts 5: 33

Stacking fault energy in precipitates

Stacking fault energy per unit area is lowered in


ppt.
Stacking fault widens;
Dislocation stacking fault energy per unit
γSF γSF length ⇑
Dislocation elastic energy per unit length ⇓
Overall dislocation energy in pptt⇓
coherent or
semi-coherent ppt

Stacking fault energy per unit area is increased in


ppt.
Stacking fault contracts;
Dislocation stacking fault energy per unit
length ⇓
γSF γSF Dislocation elastic energy per unit length ⇑
Overall dislocation energy in ppt ⇑
coherent or
semi-coherent ppt Either way, the ppts harden the material.

Microplasticity 5 – Strengthening S.G. Roberts 5: 34

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Ordered precipitates
Ni

Ni

γ` γ`

Al
0.2 µm
Ni,Fe

“Superalloys” are the classic example

Key component of the microstructure is precipitates of (Ni, Fe)3Al: γ`.


A modern superalloy might be 60 - 85% γ`
Nickel is effectively a “glue” holding the γ`together: flow is restricted by
Hall-Petch effect in narrow channels.

Microplasticity 5 – Strengthening S.G. Roberts 5: 35

Ordered precipitates

APB

coherent
ordered ppt

1) Single matrix dislocations will “reverse” the ordering, producing an Anti-phase boundary.
Matrix dislocations must “pair up” to go through.
Energy of the dislocation pair is increased by the APB.

2) Ordered structure means higher flow stress in precipitate.

3) APB may be more stable on non-glide plane – dislocation can “flip” into non-glide configuration.

Microplasticity 5 – Strengthening S.G. Roberts 5: 36

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Ordered precipitates

Anti-phase Yield stress (MPa)


boundary on (100)
600
20% γ`
Stacking fault 500
on (111) 40%
400 60%

300 80%

200 100% γ`

Ni / Ni3Al
100

0
0 200 400 600 800 1000 1200
Temperature (°C)

Transition of APB from {111} glide plane to {100} The yield stress of γ`increases with increasing
non-glide plane is thermally activated temperature (up to about 700ºC).

Microplasticity 5 – Strengthening S.G. Roberts 5: 37

Localised Obstacles
Fobst “Localised Obstacles” ≡ no long-range forces on dislocations

 Gb 2  Gb
Fobst = 2  cos φ and R=

 2 
= Gb 2 cos φ
λ
Obstacle spacing = λ
Fobst
When dislocations break away from obstacles, Fobst is as high as
2φ the obstacle can extert, and φ is a critical (minimum) value φc.

½ Gb2 τ.b λ = Fobst

Gb 2 cos φc
R τ=

Fobst Gb
= cos φc
λ
Obstacle strength is characterised by this
critical angle for breakaway, φc
τ
Microplasticity 5 – Strengthening S.G. Roberts 5: 38

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“Strong” and “Weak” local obstacles

2φc
b Weak obstacles: φc ≅ π / 2
R
λ
τ

2φc

b
Strong obstacles: φc ≅ 0

λ
τ

Microplasticity 5 – Strengthening S.G. Roberts 5: 39

Strengthening from local obstacles

What is the obstacle spacing? (Weak obstacles: φc ≅ π / 2)


Λ

A: If dislocation frees from one obstacle,


D then goes to same R, does not
λD
encounter another obstacle; continues to
“unzip” – λ tends towards λB
λC
C B: If dislocation frees from one obstacle,
then goes to same R, doesn’t quite
encounter another obstacle - λ tends
λΒ towards λC
B .
C,D: Dislocation already hitting multiple
obstacles: φc won’t be reached; λ tends
towards λA.

A What is the critical condition?

λΑ

Λ: mean particle spacing; λA etc: effective particle spacings for these dislocations

Microplasticity 5 – Strengthening S.G. Roberts 5: 40

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Strengthening from weak local obstacles


When dislocation unpins from one obstacle, it can move
forward until its curvature rises again to that before
unpinning as it encounters another obstacle.

In “Steady state”:
• τ is constant (= flow stress)
• R is constant
R • A* = area swept per obstacle passed = Λ2
A* = (area of segment, chord 2λ ) – 2.(area of segment, chord λ )
A*
(2λ )3 λ3 λ3
A * = Λ2 = −2 =
12R 12R 2R
τλ3
Λ2 =
Gb Λ
λ λ=
b (cos φc )
Gb
R but τ= cos φc
λ

τ
Gb 3
φc
τ= (cos φc )2
Λ

Microplasticity 5 – Strengthening S.G. Roberts 5: 41

“Strong obstacles” - hard precipitates

• Precipitates are very effective blocks to


dislocation motion, if:
• They are “ordered intermetallic”
compounds – strong directional
bonding (e.g. CuAl2 in Al alloys, Ni3Al in
Ni-based superalloys, Fe7Mo6 in
maraging steels)
• They are [near] covalent compounds:
e.g. Fe3C, WC, AlN in steels, MoSi2 in
Al alloys
• They have a distinct interface with the
“matrix” metal
• They have a strong associated stress
field (from partial coherency or simple
“misfit”)
• They are large, and thus difficult to cut
through.

• However, Iarger means fewer and more


widely spaced.

Microplasticity 5 – Strengthening S.G. Roberts 5: 42

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Dislocations and strong obstacles

Precipitates on
dislocation’s
slip plane

Dislocation line

Microplasticity 5 – Strengthening S.G. Roberts 5: 43

Dislocations and strong obstacles

Microplasticity 5 – Strengthening S.G. Roberts 5: 44

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Dislocations and strong obstacles

The bigger the spacing between the obstacles,


the easier it is for dislocations to squeeze through the gaps.

Each “bypass” event leaves a dislocation behind – narrowing the gaps.


Affects work-hardening rate.

Microplasticity 5 – Strengthening S.G. Roberts 5: 45

Precipitation hardening – “strong” obstacles


If the the obstacles do not allow
dislocations to pass, breakaway angle θ
approaches zero.
θ
b Loop shape can appraoach to a half-
circle; radius of dislocation curvature is a
R minimum for this obstacle spacing.

τ.b = Gb2 / 2R = Gb2 / Λ


Λ τ or if we only take component of τ in
direction of b:
τ = Gb / Λ

Λ (µm) τ (MPa)
Typically (Steels),
0.01 2250 feasible?
G = ~ 90 GPa
0.1 225 useful
b = ~ 0.25 nm
1 22.5 Not a useful
strength
10 2.25 increase

Microplasticity 5 – Strengthening S.G. Roberts 5: 46

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Precipitate – dislocation interactions in age-hardening


0.05 µm 0.5 µm 2 µm 10 µm

Yield Stress
(MPa)
semi-coherent
semi-coherent
θ′′
400 θ′
coherent
G.P. interfacial dislns, Bowing
zones “hard” ppts
Cu in incoherent
solution θ
200 Coherency Stress
ppts locally
Solute block dislocations
"base level" - pure Al

(~50hrs at 190C)
Ageing Time
(scale varies with ageing temperature)

Microplasticity 5 – Strengthening S.G. Roberts 5: 47

Stopping dislocations – Grain boundaries


z
z
y

y
x
Slip planes in both grains have common line in g.b.
x
(may happen at twin boundaries)

Burgers vector lies in g.b. plane.


b

Still may be problems if dislocation is dissociated.

z
y

x x
z
Most general case - most likely case !
b2
b
1 Direct transmission of dislocations
almost impossible.

Microplasticity 5 – Strengthening S.G. Roberts 5: 48

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Stopping dislocations – Grain boundaries


Pile up in Cu – 4.5% Al.

Every dislocation in the pile up exerts stress back on the


source - tending to stop it operating.

Slip must also be transmitted from one grain to the next .

This is assisted by a stress concentration at the head of the


pile-up.

Shear Stress τ
app

dislocation
source
dislocation
source
s
tresse
back-s

τ blocked dislocation
app

Microplasticity 5 – Strengthening S.G. Roberts 5: 49

Stopping dislocations – Grain boundaries


τ app

Stress felt by the possible new dislocation source is


proportional to the stress at the head of the pile up,
τg.b.:
dislocation

τg.b. = Ndis τdis source

d
Ndis is the number of dislocations in the pile-up;
τg.b.
τdis is the stress each "passes on" to the next one in τapp
the array.
τdis = τapp - τfrict For slip to be passed from one grain to the
next, the source must be activated at some
τfrict is the minimum stress to move dislocations within critical τ∗source. Applied stress needed:
the grain. 1
 τ* 2
The number of dislocations in the pile up is: τ*app = τfrict +  source 
 α ′′d 
Ndis = (π/Gb) d` τdis

where d' is equal to d, or d/2 - exact value not The Hall-Petch equation.
important.
so: 1

τg.b. = αd (τapp – τfrict)2 σ y = σi + k d 2

Microplasticity 5 – Strengthening S.G. Roberts 5: 50

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Hall-Petch Effect
Lower Yield Stress
(MPa)
Effect of grain size on yield
400 strength of mild steel.

Note:
¾ range of grain sizes – typical for
300
an engineering alloy
¾ (martensites may have
interfaces spaced by only a
few 10’s of nm)
200 ¾ (in pearlite, interfaces may be
a few µm apart).
¾ ~3x range in yield strength over
this grain size range
100 ¾ variation of strength with
temperature
¾relatively high σi:
1mm 100µm 10µm due to strengthening mechanisms
other than grain size.
0 2 4 6 8 10
d-1/2 (mm-1/2)

Microplasticity 5 – Strengthening S.G. Roberts 5: 51

Steels
0.15%C

10µm

50µm

Pearlite
Iron-Carbon martensites:
• many interfaces
1-10µm • interiors of “laths” heavily twinned or dislocated
• high and strongly varying local stresses -
• around each locked-in C
Pearlite (Fe/Fe3C): • between laths
• Flow in Fe lamallae restricted by • between “colonies” of different orientation
Hall-Petch
• Flow in Fe3C lamallae restricted by All these give very high resistance to dislocation motion.
its high yield stress

Microplasticity 5 – Strengthening S.G. Roberts 5: 52

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Work Hardening

e
rat
ing
rd en iron
-Ha
Work
= ε = 20%
pe
Sl o stic
Pla 1012
Stress

Disln. density (cm-2)


109
Elastic

ε = 0%

106

Strain 1
stress ∝
disln. spacing
Most dislocations are not mobile –
they are just obstacles to the few that are. = (disln. density)

Microplasticity 5 – Strengthening S.G. Roberts 5: 53

Simualtions of interactions between dislocations

When the misorientation between When the misorientation between the


the two dislocation glide planes is two dislocation glide planes is small
high and the applied stress is high, and the applied stress is small, the
the two interacting lengths are short. dislocations react over a longer length
and form junctions which are strong
obstacles to plastic flow.

http://zig.onera.fr/%7Edevincre/DisGallery/index.html
Microplasticity 5 – Strengthening S.G. Roberts 5: 54

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“Dislocation debris” formation and “Forest interactions”

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Interaction of one single dislocation


Formation of a small dipolar loop
line with the forest.
by double cross-slip (centre) of a
mobile dislocation (cyan). The The “specimen” is oriented for slip
cross-slipped portions are shown on a single slip system (cyan).
in pink. Dislocations on other systems are
below the CRSS, and act as local
obstacles to slip.

http://zig.onera.fr/%7Edevincre/DisGallery/index.html
Microplasticity 5 – Strengthening S.G. Roberts 5: 55

“Dislocation dynamics” simulation of work-hardening

Deformation of a fcc single crystal (Cu) of


linear dimension 15 µm.

The stress tensile axis is [100], the imposed


strain rate is 50 per second and the plastic
strain reached at the end of this sequence is
0.1%.

http://zig.onera.fr/%7Edevincre/DisGallery/index.html
Microplasticity 5 – Strengthening S.G. Roberts 5: 56

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“Dislocation dynamics” simulation of work-hardening

Stress
(MPa)

Strain (%)

Long range (elastic) Short range (jogs, locks)


interactions only interactions only

Copper – work hardened


to 20% strain

Materials Science and Engineering A


309-310, (2001), 211-219

Microplasticity 5 – Strengthening S.G. Roberts 5: 57

Work-hardening: single- vs. poly- crystals

Stress (MPa) Applied tensile stress σ, tensile strain ε.


120
Pure Aluminium For single crystals, on slip system
100 with resolved shear stress τ, shear strain γ:
σ
80 τ = σ cos φ cos λ =
Polycrystal M
60 At Yield: σ y = Mτ y
1
40 For polycrystals: σ y = Mτ y dε =
M
∑ dγ
20 Single Crystal
where M is averaged over all grains.

0 dσ dτ
0 0.2 0.4 0.6 0.8 1 = M2
Strain (%) dε dγ
For ccp metals, the “Taylor factor”, M ≅ 3.1

Microplasticity 5 – Strengthening S.G. Roberts 5: 58

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Workhardening and ductility

A B C D
A B C D

ε
: σ,
e”
ru
“T , e
”, s
ing
in eer
“ Eng
Stress


Critical point at C is when =σ

This is where the workhardening rate is


Strain no longer high enough to offset increase
in stress in an incipient neck.

Workhardening rate controls ductility.

Microplasticity 5 – Strengthening S.G. Roberts 5: 59

Ideal microstructure for “strength” ?


• Can’t use a non-metal as base of alloy
– could get high yield strength this way but toughness would be far too low.
• Can use work-hardening to improve strength, but:
– effectiveness very limited for materials with yield stress increased close to UTS by other means
– reduces toughness (by reducing work-hardening capacity)
– will “anneal out” at moderate temperatures
• Can use fine grain sizes to improve strength (and toughness!)
– relatively limited (but useful) strength improvement (a few hundred MPa)
– fine grain sizes no good at high temperatures
• grain size will grow
• grain boundaries are fast diffusion paths – creep strength will be poor
• Can use solution strengthening
– in bcc, interstitial solutes give a limited but useful increase in strength (+ 50 to 80 MPa)
• (most steels are well over the solubility limit for C anyway)
• can quench in excess C, N into solution in martensite. (up to + 1000 MPa)
– but this form of martensite is very brittle (all dislocations are locked)
– substitutional solutes can give moderate strength increases (a few hundred MPa)
• limited by solubility – solutes with big misfits will have low solubilities
• Can use precipitation hardening
– need to achieve a very fine dispersion of very hard precipitates (up to + 1000 MPa)
– or a very fine dispersion of weaker precipitates with strong associated strain fields (not quite so effective)

Microplasticity 5 – Strengthening S.G. Roberts 5: 60

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“Ideal” Microstructures
• Use precipitation hardening
– need as fine a dispersion as possible of particles as hard as possible.
• Topped up with solution strengthening
• Solutes may be present anyway for a variety of reasons:
• to scavenge undesirable impurities (e.g. Mn, Si, Al in steels)
• to slow down diffusional reactions and thus promote martensite
• to confer corrosion resistance (e.g. Cr in steels)
• to react with other elements present and produce precipitates
• Why not have a fine grain size anyway ?
• Generally a good idea, as toughness is improved
• (Can we make spatial variations: e.g. surface different from bulk?)

• Extra constraints if high temperature use is likely:


• base material must have a high melting point (!)
• any precipitates must be “stable” (there is a T’dynamic driving force to reduce number and increase size)
• reduce driving force (interface energy)
• slow down “coarsening” (reduce diffusion rate)
• fine grain size may not be good
• grain boundaries are fast diffusion paths so can get high creep rates
• grain size will tend to grow anyway
• beware (or use!) further reactions between elements present. εΨπ

εψπ
Microplasticity 5 – Strengthening S.G. Roberts 5: 61

What makes a metal suitable as a base for


useful alloys ?
• Readily available & cheap (bearing in mind the application)
• Cubic crystal structure
– large number of slip systems for good ductility
• Readily dissolves a wide range of substitutional and interstial solutes
– allows strong solution hardening
• Solubility of some solutes varies strongly with temperature
– allows use of precipitation reactions to form strong alloys
• Forms hard compounds with a range of elements
– precipitation of these gives strong hardening
• Undergoes an allotropic phase change (e.g. Fe, Ti)
– can cycle through phase change to produce “physically” complex microstructures
– can use partitioning of solutes between the phases to produce “chemically” complex microstructures
– can get martensitic (quenched) microstructures
• Low density
– for some applications, anyway.
• High melting point
– first step in base for high temperature alloys
• Chemically fairly stable
– either in itself, or via a strong, tenacious oxide film
• Not hazardous
– poisonous, explosive, inflammable, radioactive….

Microplasticity 5 – Strengthening S.G. Roberts 5: 62

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“The big 3”
Iron Aluminium Copper
Useful ores (bauxite)
Available? Plentiful Useful ores fairly rare
widespread
Cheap ? Needs cheap electricity to Ores tend to be “thin”.
Extraction easy with C. ~£150
(£ / tonne 1997) extract. ~£1000 Refining needed. ~£1500

M.P. (°C ) 1538 660 1084

Density (kg m-3) 7874 2700 8920

fcc only
Allotropy bcc ⇒ fcc ⇒ bcc with rising T fcc only

good solvent for many elements.


moderate solvent for many good solvent for many
Dissolves things ? Solubilty depends on allotropic
elements elements
form.
can be strong – and affected by not strongly for most
T-Variable solubilty strongly for many elements
allotropic changes elements
forms compounds with many forms compounds with forms compounds with
Compounds
elements many elements many elements
Oxidises steadily. Can be Oxidises readily to form
Stability Fairly inert.
improved by solutes. stable thin film.

Hazardous ? No. No. No.

Microplasticity 5 – Strengthening S.G. Roberts 5: 63

The “other 3”
Nickel Titanium Magnesium
“Thin” ores in Canada and Useful ores fairly common,
Available? Useful ores not plentiful
New Caledonia. also in seawater.
Cheap ? Complicated, energy intensive Needs cheap electricity to
Needs electrolysis. ~£1500
(£ / tonne 1997) extraction. ~£4700 extract. ~£10000

M.P. (°C ) 1455 1668 650

Density (kg m-3) 8908 4507 1738

Allotropy fcc only cph ⇒ bcc with rising T cph only

good solvent for many


good solvent for many moderate solvent for some
Dissolves things ? elements. Solubilty depends
elements. elements
on allotropic form.
can be strong – and affected
T-Variable solubilty can be strong can be strong
by allotropic changes
forms compounds with many forms compounds with many forms compounds with
Compounds
elements elements some elements
Oxidises readily to form Oxidises readily to form
Stability Fairly inert.
stable thin film. fairly stable film. Can burn.

Hazardous ? No. No. No.

Microplasticity 5 – Strengthening S.G. Roberts 5: 64

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Microplasticity (2nd year MSoM / MEM)


Steve Roberts
Michaelmas term
Question sheet 1

Concepts

Most of the answers to these questions are (or should be) short, but to answer the questions
properly you will have to think about, use and extend material in the lectures, not just
reproduce it! You may also have to look up some basic data.

1) Basics. Give a brief (max. 100 words, ideally less, one or two diagrams) definition of the
following:
a. A dislocation
b. A slip plane
c. A (glissile) dislocation loop
d. A force on a dislocation
e. A stacking fault formed by shear

2) More basics. Give a brief (max. 100 words, one or two diagrams) explanation of the
following:
a. How do we know dislocations really exist?
b. How does dislocation glide give rise to plastic flow?
c. Why can dislocations in some types of pure material glide at fairly low stresses?
d. Why can’t dislocations in other types of pure material glide at low stresses?
e. What might make two dislocations attract each other?

3) Nodes. Assume that all three dislocations are pure edge in the diagram below:
b1
b3
b1
1 3

b2
2

a. Sketch an “atomic plane” diagram around dislocations 2 and 3 to demonstrate that


b1 = b2 + b3.
b. If the line vector of dislocation 2 were redefined to be in the opposite sense, how
would this affect: (i) the definition of b2; (ii) the summing of the Burgers vectors?
c. Why would a node of such a type be unlikely to exist in reality?

4) Loops. Consider the dislocation loop below; what will the crystal look just after the has loop
emerged:

b
b
l l
b
b

b b

a. Only in the middle of the “left and right” faces;


b. Only in the middle of the “near” and “far” faces.
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5) Loops. Is it possible for a dislocation loop to exist for which all parts of the loop are:
a. Pure screw dislocations?
b. Pure edge dislocations?
In each case, either sketch the configuration of the loop or explain why it cannot exist.

6) Forces. Use the same methodology as for the derivation of the glide force on a dislocation to
give an equation for the climb force on an edge dislocation in a crystal subjected to a tensile or
compressive stress.

7) Forces / FSRH convention. On the diagram below, showing screw, mixed and looped
dislocations, the line vectors are not indicated. Indicate the correct sense of the line vectors to
give glide in the direction shown with the indicated shear stress (darker green indicates shear
stress directionon top to the crystal).

F
τ

8) Peach-Koehler Formula. ( F = (σb) × l ). Show that:


a. For an edge dislocation with b in the x-direction and l in the z-direction, τxy
produces a glide force (in which direction?) and σxx produces a climb force (in which
direction?), but other stress components produce no force on the dislocation.
b. For a screw dislocation with b and l in the x-direction, τxy and τxz produce glide
forces (in which directions?), but other stress components produce no force on the
dislocation. -
c. For an edge dislocation with b in the [110] direction and l in the [110] direction, τxz
produces a glide force (how large, and in which direction?), but τxy produces no glide
force.

9) Dislocation energies and interaction stresses. Download the spreadsheet “dislnpair.xls”


from my website at http://users.ox.ac.uk/~roberts/sgrgroup/index.htm. Use this to plot the
energy of a pair of like (or unlike) dislocations at various separations on the same slip plane.
Show that the energy of the system varies in the expected way with separation, giving rise to a
force between the dislocations that varies inversely with their separation.
Experiment with different configurations (dislocations separated in the direction of b, normal
to b, moving on parallel planes, etc.)
(NB – the energy is given in “arbitrary units”, and only sums up the energy within the area
plotted on the graphs. Dislocations close to the edge of the plot area will “lose” energy).

10) Dislocation interaction stresses. Consider two parallel edge dislocations with identical
Burgers vector b on glide planes separated “vertically” by 10b.
a. Plot the force acting on one of these dislocations as a function of “horizontal”
separation ranging from –50b to +50b.
b. What equilibrium separations are possible?
c. What equilibrium separations are possible if the dislocations have parallel Burgers
vectors of opposite sign?
d. Compare the way these stresses vary with position with a plot of dislocation energy
vs mutual position for this configuration, using the spreadsheet introduced in Q9.
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11) Image forces.


a. “Pure” copper has a minimum shear stress to move dislocations of ~10 MPa. If a thin
foil of copper is examined in a TEM, how thick a specimen is needed to have a
reasonable chance that it contains any dislocations?
b. If the foil were of a single crystal of magnesium (HCP), how could you align the foil
to prevent the dislocations leaving it due to image forces?
c. What forces will a dislocation feel if it is close to a surface covered in a thick layer of
oxide, which has a much higher modulus than the bulk metal?

12) Peierls stress. Explain in qualitative terms (no equations!) why dislocations with wide cores
need less applied stress to move them.

13) Thompson’s tetrahedron: …. First make your tetrahedron…..


a. To move the dislocations so as to form the Lomer-Cottrell lock as illustrated in the
lecture, in what direction would one have to apply (i) a compressive stress (ii) a
tensile stress ?
b. There are three other possibilities similar to the Lomer-Cottrell lock for combinations
of positive and negative b1 and b2. Use the Thompson’s tetrahedron notation to
follow the course of these reactions, and comment on the stability or otherwise of the
reaction products.
c. If the stacking fault energy were so high as to effectively prevent dissociation, what
possible reactions could occur ? Is the most stable product more or less stable than
for the most stable “dissociated” product? Is it mobile (“glissile”) or immobile
(“sessile”)?

14) Frank loop conversion and prismatic loops:


a. Use a “side view” of the {111} planes, labelling the “ABC” stacking, to show what
happens to the stacking during the conversion of a Frank loop to a prismatic loop by
a Shockley partial (3 drawings will be needed: “before”, “half-way” and “after”).
b. What are the energetics of the conversion?
c. Explain qualitatively why the conversion can only happen in the loop is above a
certain critical size. (A quantitative calculation about this will be found on Q-sheet 2)
d. If the prismatic loop is subjected to a high enough stress to make the dislocation
glide, what will it do ?

15) Dislocations in bcc metals:


a. For a dislocation with b = ½ a [111], list all the possible slip planes.
b. On a drawing of one or more bcc unit cells, draw in one possible slip plane of each
type ({110}, {112} and {123}) for b = ½ a [111].
c. Explain why slip lines in bcc metals are “wavy” (why aren’t they in ccp metals?)
d. Which type of dislocation (edge or screw) controls the stress-strain response of a
“pure” bcc metal? Why ?

16) Dislocations in ordered intermetallics: TiAl is an “up & coming” lightweight structural
-
material. It has the L10 crystal structure (tetragonal, c/a =1.02). It slips on {111}<110>
systems.
a. Sketch the atomic arrangement on the slip plane.
b. What kinds of dislocations and associated stacking faults might exist in this
structure?

17) Dislocations in ionic materials:


a. The lecture handout shows the “lowest energy” atomic arrangement at the core of an
-
{110}<110>edge dislocation in the rock-salt structure. Sketch likely atomic positions
for 2 or 3 intermediate positions as the dislocation glides to the next “lowest energy”
position.
-
b. How many {110}<110> slip systems are there ? How many are likely to be
independent? What effect will this have on the deformation behaviour of (say) MgO?
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18) Dislocations in covalent materials:


a. A dissociated dislocation loop in silicon is shown in the lecture notes. What will be
different about it if a similar loop is formed in gallium arsenide? (Hint: try drawing a
section of the loop as seen “edge on” down <110>, labelling the atoms Ga and As
carefully.)
b. Silicon is (relatively!) ductile only above about 700ºC. What might the lowest
temperatures for some ductility be in (i) germanium and (ii) diamond?
c. The lecture notes show dislocation velocity / stress data for silicon. How might these
have been obtained?
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Microplasticity (2nd year MSoM / MEM)


Steve Roberts
Michaelmas term

Strength of materials: Concepts

Most of the answers to these questions are (or should be) short, but to answer the questions
properly you will have to think about, use and extend material in the lectures, not just
reproduce it! You may also have to look up some basic data.

1) Yield stress and bonding. At roughly what temperature would you expect:
a. Diamond to have a hardness of 20 GPa.
b. Nickel to have a yield stress of 100 MPa.
c. Molybdenum to have a yield stress of 250 MPa.
(Diamond: room temperature hardness, 45 GPa. For metals, hardness = ~ 3x yield stress.
Other relevant information can be found at www.webelements.com and in the lecture
handouts.)

2) Samples of a well-annealed pure cubic-close packed metal are taken to 70% of its melting
point and cooled rapidly by quenching. Tensile tests give yield strength values that decrease
over several days, reaching a stable value a little below that for un-heat-treated samples.
Explain what is happening, and what hardening mechanisms operate.

3) Diffuse obstacles. Describe and explain the differences in the ways dislocations interact with
“Weak diffuse” obstacles and “Strong diffuse” obstacles.

4) Modulus effects: Explain why a material is hardened by solute atoms that produce a local
change in modulus, irrespective of whether the modulus is increased or decreased.

5) Strain ageing:

a. Tensile testing can be done in either “load control” (load is increased steadily,
extension is measured) or “displacement control” (extension is increased steadily,
load is measured). Which mode should be used to investigate strain ageing, and why?
b. What is happening in the near-horizontal part of the 20ºc stress-strain curve for a
plain carbon steel shown below?
c. As temperature rises, stress-strain curves in iron-carbon alloys pass can become
“serrated” (see below, 100ºC - 200ºC). Explain why this happens, and why the
serrations disappear as the temperature rises further (≥250ºC).
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6) Coherency stress hardening. Starting with aluminium with 4 wt% copper dissolved as a
random solid solution, plot the expected hardening due to coherency stresses as the solutes
form Guiner-Preston zones.

7) Local Obstacles. Describe and explain the diffenences in the ways dislocations interact with
a. Diffuse obstacles and local obstacles
b. “Weak” local obstacles and “Strong” local obstacles

8) Precipitation hardening. Describe and explain the differences in the ways dislocations
interact with coherent precipitates, semi-coherent precipitates and incoherent precipitates.

9) Precipitation hardening. In Al-Cu alloys,, what interactions between dislocations and


precipitates contribute to the hardening effects produced by

a. Guinier-Preston zones
b. θ`` precipitates
c. θ``precipitates
d. θ precipitates

10) Work-hardening: Compare and contrast the likely work-hardening behaviour of


polycrystalline specimens of:

a. magnesium
b. aluminium
c. aluminium 4% Cu, quenched and aged at 180ºC for 10 hours.
d. aluminium 4% Cu, quenched and aged at 180ºC for 500 hours.
e. iron
f. iron 0.2% carbon, “normalised”
g. iron 0.2% carbon, “quenched and tempered”

11) Alloy design for strength: The nickel-based superalloy MAR M200 has the following
composition: 9% Cr, 10% Co, 1.5% Ti, 5.5% Al, 0.15% C, 0.05% Zr, 0.015% B, 10% W,
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2.5% Ta, 1.5% Hf, balance Ni. Describe the rôle(s) of the underlined elements in
strengthening the alloy.
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Microplasticity (2nd year MSoM / MEM)


Steve Roberts
Michaelmas term
Question sheet 2
Problems

1) “Pure” aluminium has a Young’s modulus of 70 GPa, a Poisson’s ratio of


0.24, a lattice parameter of 0.404 nm and a critical resolved shear stress to
move dislocations of 10 MPa.

(a) What is diameter of the smallest dislocation loop, with Burger’s vector in
the plane of the loop, that can exist in aluminium?

(b)For such a loop of twice this minimum diameter, what level of resolved
shear stress would be needed:
(i) to make it expand
(ii) to make it contract?

For each of b(i) and b(ii), what will happen once dislocation motion starts if the
stress is kept at the same level?

You can try to solve part (a) either roughly, by assuming that the line tension
of the dislocation line in a loop, radius R, is the same as that for an infinite
straight dislocation, or in a more sophisticated way, by taking:

E = [Gb2 / (4πα)]. ln(R/b). ………. (α = 1 or (1-υ) – use either)

The latter approach may need use of numerical methods.


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2) For a pure edge dislocation, with line vector along the z-direction, show (by
transformation of the stress field as expressed in Cartesian co-ordinates) that:
− Gb sin θ
σ rr = σ θθ =
2π( 1 − ν ) r
Gb cos θ
σ rθ =
2π( 1 − ν ) r
− Gbν sin θ
σ zz =
π( 1 − ν ) r
Gb( 1 + ν ) sin θ
P=
3π( 1 − ν ) r

3) Show that the non-core line energy per unit length E of a dislocation with
Burgers vector b inclined at an angle θ to the dislocation line is:

Gb 2 ( 1 − ν cos 2 θ ) ⎛ R ⎞
E= ln⎜⎜ ⎟⎟
4π( 1 − ν ) ⎝ r0 ⎠
(you may assume the standard results for pure screw and pure edge
dislocations).

4) An ionic solid made up of equal amounts of two elements has the NaCl
crystal structure. The solid melts at 850°C. At room temperature it can deform
on {001}<110> slip systems with a critical resolved shear stress of 1050 MPa,
and on {110}<1 1 0> slip systems with a critical resolved shear stress of
120 MPa.

(a) Why does slip not occur on {111} planes in this crystal structure? [3]

(b) Why do the critical resolved shear stresses for the {001}<110> and
{110}<1 1 0> slip systems differ by so much? [3]

(c) At what value of applied stress will a single crystal of the ionic solid start to
deform if it is loaded in compression:
(i) along the [111] direction [4]
(ii) along the [100] direction? [4]
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(d) What is likely to happen if a polycrystalline specimen of the ionic solid is


tested in compression to a plastic strain of 5%:
(i) at room temperature [3]
(ii) at 650˚C? [3]
[EMS finals 2000]

5. (a) Two straight edge dislocations with parallel Burgers vectors lie on
parallel slip planes 30 nm apart. If the shear modulus G is 60 GPa, the
magnitude of the Burgers vector b is 0.3 nm, and the Poisson ratio υ is 0.3,
calculate the minimum resolved shear stress on the slip plane required to
force the dislocations to glide past each other. [12]
The following information may be of use:
The stress field of a straight edge dislocation along the z-axis, with a Burgers
vector in the x-direction, has non-zero components:

σ xx = −
(
Dy 3 x 2 + y 2 ),
(x 2
+ y2 )
2

σ xy =
(
Dx x 2 − y 2 ),
(x 2
+y )
2 2

σ yy =
(
Dy x 2 − y 2 ),
(x 2
+y )
2 2

(
σ zz = σ σ xx + σ yy , )
Gb
where D =
2 p(1 − n )

(b) Giving reasons, describe what would happen if:


(i) one of the edge dislocations were replaced by a screw dislocation [4]
(ii) both dislocations were replaced by screw dislocations. [4]
[MSoM finals 2000]
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6) Two edge dislocations on parallel planes, with mutually perpendicular


Burgers vectors of the same magnitude b, pass close to each other as shown:

Show that the maximum climb force exerted between the two dislocations is:
νGb 2 ,
Fmax =
π( 1 − ν )d
where d is the separation of their slip planes.
At what points on the dislocations is this climb force exerted?
At what points on the dislocation is the climb force zero?
What will happen if the temperature is raised enough for climb to occur?

[NB: Error in previous versions, with a rogue factor of 4 in the maximum climb
force. Thanks to RIT for pointing this out. SGR 23/10/07]

7) By resolving the partial dislocations into their screw and edge components,
find the equilibrium stacking fault width in copper for (a) a dissociated screw
dislocation (b) a dissociated edge dislocation. How do these results compare
with the “rough” value of 3.7 nm derived in the lectures?

For copper, G = 48 GPa, γ = 70 mJ m-2, b = 0.256 nm.


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8) [An expanded variant of the question set in finals in 2005]

y A

x
B

a ) The diagram shows an edge dislocation (with Burgers vector in the x


direction and line vector along z) close to two substitutional solute atoms in
positions A and B.

In of the following two cases, outline the mechanism of interaction (if any)
between the dislocation and the solute atom at A, and the effect on the
material’s flow stress:

(i) the solute atoms are smaller than the matrix atoms, but do not change
the matrix’s elastic moduli;

(ii) the solute atoms are the same size as the matrix atoms, but locally
reduce the matrix’s elastic moduli.

b) How would the interactions for cases (i) and (ii) above change if the solute
atom were at position B rather than position A?

c) Unobtanium (Ut) is a cubic-close packed metal with atomic diameter


d = 0.537 nm and Young’s modulus 180 GPa. The following solutes are
available:

Solute (X) Atomic Young’s Modulus of Solubility Limit in Ut


diameter (nm) Ut-10% X (GPa) (at% X)
Dullium (Du) 0.472 180 10
Petitbonum (Pe) 0.537 172 35
Chewingum (Cg) 0.541 172 18
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Pure unobtanium has yield stress of 25 MPa.


A solid solution of Ut – 10%Du has a yield stress of 70 MPa.
A solid solution of Ut – 30%Pe has a yield stress of 36 MPa.
(all the above materials have the same grain size).

What is the maximum increase in yield stress for a material of this grain size
that could be produced by adding chewingum in solid solution to unobtanium?
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Microplasticity
Past Finals (General paper) Questions
(NB – the course has changed somewhat over the years. Nonetheless, even the
earlier questions are good exercises in the topics covered in the SGR 2007/8 variant
of this course)

2007

1. a) Give brief explanations for two of the following experimental observations:


(i) Slip in many body-centred cubic metals does not follow Schmid’s law.
(ii) The room temperature ductility of copper is increased by the addition of
30wt% zinc.
(iii) The addition of a few tens of parts-per-million of Cr2O3 impurity to MgO
considerably increases its flow stress.
(iv) The flow stress of the ordered intermetallic compound Ni3Al increases
from ~80MPa at room temperature to ~350Mpa at 600ºC.
[6]

b) A sample of gold is quenched to room temperature from 90% of its melting point, and
then examined by transmission electron microscopy. Small discs are seen, with contrast
indicating that each is a stacking fault bounded by a dislocation. The specimen is
examined several weeks later, and many of the discs seen previously now appear as
dislocation loops with no stacking fault. Explain these observations.
[6]

c) Careful analysis of the specimen observed in (b) showed that the dislocation loops that
had “lost” their stacking faults were all greater than 48nm in diameter. Explain why
dislocation loops smaller than this are stable against loss of their stacking faults, and
hence calculate a value for the stacking fault energy of gold.
[8]

[Gold: shear modulus = 27GPa;


lattice parameter = 408pm]

2.

A
B
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The micrograph shows a cross-section of an indentation made with a spherical indenter in


a specimen of Fe-0.02%C; the section was made normal to the indented surface and cuts
mid-way through the indentation impression. The specimen was annealed at 700ºC for 40
minutes, then polished and lightly etched.

A series of hardness tests was made along the line A-B. Results are shown in the graph
below.
500

A B
Hardness (MPa)

450

400

350

300

250
0 2 4 6 8 10 12 14 16 18
Distance along line (mm)
a) Give an outline explanation for the hardness results.
[4]

b) The grain size at a position on the line 9mm from position A was measured as 150 μm
and the grain size 3 mm from position A was 1500 μm. Estimate the grain size at position
A.
[8]
c) Sets of specimens of an Al-4%Cu material were heat-treated by being held at 550ºC
for 30 minutes, and quenched into water. They were then aged at 180ºC for either 10
hours or for 50 hours.

Tensile test results after ageing were:


Material Yield stress Ultimate Tensile Strain at
(MPa) stress (MPa) fracture (%)
Al-4% Cu (10 hours) 270 420 30
Al-4% Cu (50 hours) 425 475 12

Explain the different behaviour of these different sets of specimens in terms of the
strengthening and work-hardening mechanisms operating.
[8]
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2006

1 a) Explain why interstitial solutes such as carbon and nitrogen can give substantial
strengthening if dissolved in body centred cubic metals, but give a lower degree of
strengthening if dissolved in cubic close packed metals.
[4]

b) Describe how you would expect the yield strength of a metal to vary with grain size.
[2]

c) Describe how you would expect the yield strength of a metal to vary with precipitate
size, if the precipitates are incoherent and formed by reaction between the matrix metal
and a solute that has negligible room temperature solubility.
[4]

d) The table below gives results of microstructural examination and tensile testing on an
alloy aged for the given times. The alloy contains intragranular precipitates as a result of
the aging.

Aging time (hr) Grain size (μm) Precipitate size Precipitate type Yield Strength
(nm) (MPa)
2 25 13 coherent 231
10 43 22 semi- coherent 269
20 54 27 semi- coherent 315
50 74 37 incoherent 430
75 83 41 incoherent A
100 93 46 incoherent 367
500 159 79 incoherent 266
1000 200 100 incoherent 235

Assuming the effects of grain size and of precipitates on yield strength are simply
additive, calculate the unknown yield strength A, and the contribution of each type of
strengthening. Give your answer to 3 significant figures.
[10]
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2. a) Explain briefly why:


i) screw dislocations in body centred cubic metals cross-slip more easily
than those in cubic close packed metals
ii) in a body centred cubic metal, screw dislocations have lower mobility than
edge dislocations.
2 x [3]

b) Two parallel edge dislocations, of Burgers vector b, lie on parallel glide planes that are
separated by a fixed distance Δy, as shown.

i) Sketch a graph showing the variation of interaction glide force, F, between


the two dislocations for -5Δy < Δx < 5Δy. State, with reasons, which
positions of equilibrium are stable and which are unstable. (Note equations
for the stress field from an edge dislocation given below).
[8]
ii) Explain what happens to F if the sign of the Burgers vector of the upper
dislocation is reversed.
[3]
iii) What would be the effect on F of replacing the upper edge dislocation
with a screw dislocation? Why?
[3]

Stress field components at position x, y from an edge dislocation situated at x = 0, y = 0


with line direction along z and Burgers vector b along x. G is the shear modulus and ν is
Poisson’s ratio.
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2005

1. The diagram below shows an edge dislocation (with Burgers vector in the x direction
and line vector perpendicular to the page) close to a substitutional solute atom in either
position A or position B.

a) In each of the following two cases, outline the mechanism of interaction (if any)
between the dislocation and a solute atom at A, and the effect on the stress required to
move the dislocation past the atom by glide:
i) the solute atom is smaller than the matrix atoms, but does not change the
elastic constants of the matrix;
ii) the solute atom is the same size as the matrix atoms, but locally reduces
the stiffness of the matrix.
[8]

b) How would the interactions for cases (i) and (ii) above change if the solute atom were
at position B rather than position A?
[5]

c) The following solutes are available, neither of which changes the elastic modulus
significantly:

The Um-rich ends of the corresponding Um-X binary phase diagrams are as follows:
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Which solute is able to give the greatest amount of solid solution strengthening at room
temperature, and by what factor does this amount exceed that obtainable using the other
solute (answer to 2 significant figures)?
[5]

d) Briefly discuss one additional strengthening mechanism that may be obtainable in Um-
Du alloys, and suggest a suitable alloy composition with which to investigate this
possibility.
[2]
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2004

1. a) Precipitates can increase the flow stress of a material, even when dislocations can
pass through the precipitates. Outline three distinct mechanisms by which this can occur.
[6]

b) Explain how the strength of interaction between precipitates and dislocations can be
characterised by a critical angle φc and show that the stress τ required to move a
dislocation through an array of such obstacles with spacing λ is given by:

Gb
τ= cos φ c
λ
where G is the shear modulus of the material and b is the magnitude of Burgers vector of
the dislocation.
[6]

c) A material with G = 70GPa and b = 0.25 nm contains an array of coherent precipitates


with the same lattice parameter as the matrix. At an early stage of ageing when the
precipitate diameter is 20 nm and the mean particle spacing is 100 nm, the critical angle
φc = 35º.
(i) Calculate the flow stress inside the precipitates.
[5]
(ii) The precipitates coarsen with further ageing; calculate the maximum size of
precipitates that can be cut by dislocations.
[3]

2. a) Explain why dislocations in cubic close packed metals are often dissociated, while
those in body centred metals are normally undissociated.
[6]

b) A transmission electron microscope is used to study dislocations in a pure single


crystal cubic close packed metal with lattice parameter a = 0.388 nm, shear modulus G =
46GPa and Poisson’s ratio υ = 0.31. The plane of the thin foil specimen is (111). A
dissociated screw dislocation with line vector along [110] on a (111) plane is observed to
have a stacking fault width of 3.2 nm. By resolving the partial dislocations bounding the
stacking fault into edge and screw components, calculate the stacking fault energy of the
material.
[10]

c) The foil is subjected to a shear stress in its plane and parallel to the [121] direction.
How will the dislocation in (b) respond?
[4]
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Note that the force per unit length F between two parallel dislocations of Burgers vector
of magnitude b, separated by a distance d, in a material with shear modulus G is given
by:
Gb 2
F=
2πd (1 − x )
where x = 0 for a screw dislocation and x = Poisson’s ratio υ for an edge dislocation.
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2003

1. a) In each of the following cases, describe without the use of an equation how the
energy of a pair of parallel dislocations on a single, common glide plane varies with
separation and interpret the variation in energy in terms of forces on the dislocations if:
i) the dislocations are identical and of edge character
ii) one dislocation is pure edge and the other pure screw.
[4]

b) Two parallel screw dislocations of opposite sign are lying on parallel glide planes as
shown in the diagram.. The glide planes are a distance d apart and the separation of the
dislocations, as measured in the glide planes, is z. Derive an expression for the
component of force in the glide plane on unit length of dislocation.

[8]

At what values of z is the force in the glide plane (i) zero (ii) a maximum?
[4]

c) What will be the likely outcome if initially, x >> d and the glide component exceeds
the frictional force, and if:
i) the material has a close-packed hexagonal crystal structure with a high c/a
ratio
[2]
ii) the material has a body-centred cubic crystal structure?
[2]

2. a) Discuss the interactions between dislocations and solute strains, and the
consequential effects on yield strength. Distinguish carefully the differences between
interactions with edge dislocations and interactions with screw dislocations for certain
point defects.
[10]
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b) A face-centred cubic metal has a shear modulus of 210 GPa and lattice parameter 352
pm. Various solutes are added to strengthen the material by solid solution and the
following data pertain:

Solute Atomic radius, pm Solubility limit, at%


A 124 13
E 125 19
G 143 4
J 145 3

L 91 0.08

Giving reasons for your choice; which alloying element is likely to give the greatest
increase in strength? Justify any assumptions made.
[10]
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2002

1. a) Explain why dislocations in aluminium dissociate into partial dislocations.


[5]

b) In an intermetallic compound with a cubic structure, the dislocations dissociate into


partials separated by an anti-phase boundary (APB) according to:

a[110] → a/2 [110] + a/2 [110]

Calculate the separation of the partials when a screw dislocation dissociates if the APB
energy is 40 mJm-2, the shear modulus of the crystal is 52 GPa and its lattice parameter is
0.4 nm.
[3]

c) With reference to the operative dislocation mechanisms, discuss the variation with
temperature of the flow stress of:
i “pure” iron
ii pure nickel
iii Ni3Al
[6]

5. a) What is meant by work hardening in a ductile, crystalline material?


[3]

b) Write briefly on the work hardening processes involved when glide dislocations
interact with the following:
(i) other dislocations
(ii) incoherent particles
[7]

c) A single crystal of a fcc alloy with stress axis along [123] is deformed in tension. The
yield stress is 400 MPa and electron microscopy shows that the crystal contains a uniform
dispersion of incoherent spherical particles 20 nm diameter. The shear modulus of the
crystal is 70 GPa and the lattice parameter, 0.36 nm; calculate the spacing of the particles.
[10]
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2001

1. a) Show that in a work-hardened polycrystalline sample, the yield stress, τy is given by:
τ y = τi + kρ
1
2

where, τi is the lattice resistance stress, k is a constant and ρ is the dislocation density.
[8]
b) Discuss what happens
(i) when two screw dislocations, each with line direction perpendicular to the
slip plane of the other, intersect on perpendicular slip planes;
[4]
(ii) when two 600 mixed dislocations, each with line direction perpendicular
to the slip plane of the other, intersect on perpendicular slip planes.
[5]

c) Which, if either, of the interactions in (b) can give rise to hardening?


[3]

2. a) Explain carefully what is meant by force on a dislocation when it is placed in


uniform stress field. Does a vacancy experience is such a force in uniform stress field?
Explain your answer.
[6]

b) Consider a dislocation loop on a particular slip plane. Let τ be the shear stress resolved
on the slip plane in the direction of the Burgers vector. Show that the force exerted on the
dislocation is everywhere normal to the dislocation line and that the force per unit length
dislocation is τb where b is the magnitude of the Burgers vector.
[9]

c) A straight dislocation has a Burgers vector (bx, by, bz) = (b,0,0). The dislocation is
subjected to the uniaxial stress σxx. For each of the following line directions state whether
a force is exerted on the dislocation, and if so whether it would move by glide or climb:
i) (0,0,1)
ii) (1,0,0)
[5]
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2000

1. a) Describe four mechanisms by which interactions between dislocations and particles


control the yield stress of an age-hardening alloy.
[4 x 3]

b) Show that the resolved shear stress required to sustain a dislocation with a radius of
curvature R is of order Gb/R, where b is the magnitude of the Burgers vector and G is the
shear modulus. Hence explain the decrease of the yield stress during overageing.
[8]

2. a) Two straight edge dislocations with parallel Burgers vectors lie on parallel slip
planes 30 nm apart. If the shear modulus G is 60 GPa, the magnitude of the Burgers
vector b is 0.3 nm, and the Poisson ratio ν is 0.3, calculate the minimum resolved shear
stress on the slip plane required to force the dislocations to glide past each other.
[12]
The following information may be of use:
The stress field of a straight edge dislocation along the z-axis, with a Burgers vector in
the x-direction, has non-zero components:

σ xx = −
(
Dy 3 x 2 + y 2 ), σ =
(
Dx x 2 − y 2 ), σ =
(
Dy x 2 − y 2 ),
(x 2
+y )
2 2
xy
+y (x 2
)
2 2
yy
(x 2
+y )
2 2

(
σ zz = v σ xx + σ yy ) , where D =
Gb
2π(1 − v )
.

b) Giving reasons, describe what would happen if


i) one of the edge dislocations were replaced by a screw dislocation
[4]
ii) both dislocations were replaced by screw dislocations.
[4]
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1999

1. a) What are the similarities and differences between the stress fields around screw and
edge dislocations?

A screw dislocation lying along the z-axis has a stress component σy = Gb / 2πx a
distance x from its core, where G is the shear modulus and b the Burgers vector. By
evaluating the work done in the xy plane forming the dislocation, show that the elastic
energy per unit length between radii R and r0 is given by

Gb R
= ln
4π r0

b) Explain how this leads to a dislocation line tension T = αGb2, where α is a constant.

c) A certain metal has a dislocation friction stress τF. Find the minimum size of
dislocation loop that can be stable if G = 50 GPa, b = 3 x 10-10 m and τF = 107 Pa.

2. a) Two edge dislocations with Burgers vector b of opposite sign move freely on
parallel planes. If the position of one relative to the other is given in polar coordinates
(r, θ), find the value of θ at which stable equilibrium will occur.
[10]

b) What will happen if screw dislocations replace the edge dislocations?


[4]

c) If an f.c.c. metal is alloyed with a small percentage of a substitutional element, what


differences would this make to the behaviour of (i) edge and (ii) screw dislocations?
[6]

[In polar coordinates, the components of force between two edge dislocations of Burgers
vector b in a material of shear modulus G and Poisson ratio ν are

− Gb 2 Gb 2 sin 2θ
Fr = ; Fθ =
2πr (1 − v ) 2πr (1 − v )

where the angle θ is measured from a direction parallel to the Burgers vector.]
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1998

1. a) Show that the theoretical shear strength of τth of a crystal is given by:
1 μ
τth
a 2π
where μ is the shear modulus, a the spacing of the crystal lattice and l the periodicity of
the lattice in the sliding direction.
[8]

b) Consider a single crystal cube of side R subjected to a shear stress τ. Show that, for
this cube to deform by a dislocation mechanism, the stress must reach a value of
approximately:
μb
τ=
R
where b is the magnitude of the Burgers vector of the dislocation. State any assumptions
you make.
[9]

c) Show that there is a lower limit on the size of the cube below which the cube will not
deform by a dislocation mechanism.
[3]
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1997

1. a) Write down the components of stress that tend to make:


i) an edge dislocation glide,
ii) an edge dislocation climb and,
iii) a screw dislocation cross slip.
[6]

b) Discuss three mechanisms by which particles may interact with dislocations to produce
strengthening of a metallic alloy. Under what conditions does each mechanism apply?
[10]

c) Calculate the mean particle separation in an overaged Al-Cu alloy when the yield
stress is 500MPa.
[4]

(You may assume that the shear modulus is 40 GPa and the lattice parameter is 0.356
nm.)

2. a) Derive the displacement, strain and stress fields of a screw dislocation under
isotropic elastic conditions. Hence, obtain an expression for the energy per unit length of
the dislocation.
[8]

b) Screw dislocations in b.c.c. iron tend not to interact with substitutional atoms such as
sulphur. However, they do interact with carbon interstitials. Explain these observations.
[7]

c) Would you expect the observations in (b) above to apply to edge dislocations in b.c.c.
iron? If so, why?
[5]
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1996

1. Describe the dislocation reactions which occur during the formation of a Lomer-
Cottrell lock in an f.c.c. crystal undergoing plastic deformation.
[8]

Discuss the transition from stage I to stage II in the work hardening behaviour of an f.c.c.
metal single crystal during uniaxial tensile deformation and explain why the onset of the
transition is dependent on the initial orientation of the tensile axis
[8]

Why is stage II not reached before fracture occurs for some h.c.p. metal single crystals?
[4]

2. What are the essential assumptions in the Friedel statistical model of strengthening
caused by small obstacles?
[4]
Assuming a distribution of obstacles as a square array on the slip plane which is
subjected to a shear stress t, explain qualitatively how the spacing between obstacles
pinning a dislocation depends on the obstacle strength, F.
[6]

For spherical particles explain the physical mechanisms causing the force F for two of the
following:
i) Coherency (strain) hardening.
ii) Order hardening.
iii) Stacking fault hardening.
iv) Modulus hardening.
[5+5]

3. What are the physical origins of the interactions between point defects and dislocations
in metals and in ionic crystals?
[4]

Explain how these interactions give rise to the following:


i) Cottrell atmospheres.
[4]
ii) The yield drop.
[4]
iii) Strain ageing.
[4]
iv) The Portevin-Le Chatelier effect.
[4]
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4. a) Derive the displacement, strain and stress fields of a screw dislocation under
isotropic elastic conditions. Hence, obtain an expression for the energy per unit length of
the dislocation.
[8]

b) Screw dislocations in b.c.c. iron tend not to interact with substitutional atoms such as
sulphur. However, they do interact with carbon interstitials. Explain these observations.
[7]

c) Would you expect the observations in (b) above to apply to edge dislocations in b.c.c.
iron? If so, why?
[5]
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1995

1. Write short notes on four of the following:

a) the strain-rate dependence of the flow-stress in b.c.c. metals;

b) stage I work-hardening in copper;

c) Cottrell ‘atmospheres’;

d) twinning in hexagonal metals;

e) the strength of cold worked α-brass after low-temperature annealing.


[5] x 4

2. a) Some metals contain small bubbles of gas or voids and the tensile stress is known to
increase with increasing density of bubbles within the grain. If dislocations cut through
the bubbles discuss the strengthening mechanism and derive an expression for the
interaction force.
[8]

b) A bubble density of 2 x 1010 mm-3 is found to increase the yield stress by 100 MPa;
what bubble density is needed to achieve an increase of 200 MPa if Friedel’s weak point-
obstacle criterion is applicable?
[12]

3. Explain how vacancies in a fcc metal can condense to form Frank dislocation loops,
and how the Frank loop can be converted into a prismatic loop with unit Burgers vector.
[8]

Find the critical size of a circular Frank loop in copper at which conversion to a prismatic
loop is energetically favourable.
[10]

How may such loops be introduced into metals in practice?


[2]

[Assume that the elastic strain energy per unit length of dislocation line is given by
μb 2 ⎛ r ⎞
ln⎜ ⎟ where μ is the shear modulus (45 GPa for copper), r is the radius of the loop
4π ⎝ b ⎠
and b the magnitude of the Burgers vector. The lattice parameter of copper is 360 pm and
the stacking fault energy is 40 mJ m-2].
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1994

1. Write notes on four of the following:

a) line tension of a dislocation

b) stacking faults in an fcc structure

c) Frank-Read sources

d) dislocation climb

e) Lomer-Cottrell dislocations.

2. Compare and contrast the Peierls stress in body-centred cubic and in close-packed
hexagonal metals. Discuss mechanical twinning in these structures.

3. Derive an expression for the energy per unit length of a screw dislocation lying along
the axis of a long, hollow cylinder of elastically isotropic material with inner and outer
radii r and R respectively. State the equivalent expression for an edge dislocation, and
hence derive an expression for the energy per unit length of a mixed-character dislocation
with Burgers vector b at an angle θ to the line direction. For a dislocation in a real crystal,
discuss the factors determining the magnitudes of the parameters r and R in practice.

When a sample of cold-worked copper is recrystallised, 1 MJ m-3 of energy is released;


estimate the dislocation density in the sample.

(For copper, the shear modulus is 40 GPa and the lattice parameter is 360 pm.)
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1993

1. Sketch tensile stress-strain curves to illustrate the effect of the following


dislocation/solute atom interactions:
i) dislocation locking,
ii) friction stress effects.

In (i) explain why an initial decrease in load occurs at the onset of plasticity.

In (ii) discuss the factors which may determine the force exerted upon a dislocation by an
individual solute atom, illustrating your answer with examples from copper-based solid
solutions.

2. Explain Thompson’s notation for describing the slip planes and Burgers vectors of
whole and partial dislocations in the fcc structure.

Thompson’s tetrahedron is chosen so that face α is (111), face δ is (111) and BC =


½ [110]. A dislocation moving on plane α with line direction BC and Burgers vector BD
encounters a parallel dislocation moving on plane δ with Burgers vector AB. Discuss the
interactions which occur when the dislocations meet along the line of intersection of the
slip planes (a) when they are undissociated, and (b) when they are dissociated into
Shockley partial dislocations separated by a ribbon of intrinsic stacking fault.

3. Draw a graph illustrating the work hardening behaviour of a single crystal of an fcc
metal deformed in tension. Describe in outline how the form of the graph may be
accounted for in terms of the dislocation interactions taking place.

Discuss the effect of the following upon the form of the graph:
i) crystal orientation,
ii) stacking-fault energy,
iii) temperature of deformation.
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1991

1. Explain what is meant by (a) Schmid’s critical resolved shear-stress law, and the
Schmid factor. In what circumstances might you expect Schmid’s law to be obeyed?

The structure of corundum, Al2O3, is hexagonal with oxygen atoms in hexagonal close
packing and the aluminium atoms filling two thirds of the octahedral interstices. Slip
occurs on the basal plane in a <10 1 0 > direction. How does this slip system compare
with that in zinc? Give reasons for any differences.

The a[10 1 0 ] unit dislocation in corundum dissociates into partials

a[10 1 0] → [10 1 0] + a [10 1 0] + a [10 1 0]


a
3 3 3
Calculate the separation of the partials when the dislocation dissociating is a screw.

[For corundum, the stacking-fault energy is 0.32 J m-2, the lattice parameter, a, is 0.476
nm, and the shear modulus is 156 GPa.]
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1990

1. Compare the typical forms of the tensile stress-strain curves of single crystals and
polycrystals of fcc metals and account briefly for the main features of the curves. Discuss
the effect of grain size on the stress-strain curve of the polycrystal.

Fluorite (fcc Bravais lattice) slips only on the systems {001} <1 1 0 > at low
temperatures. Discuss the probable behaviour in a tensile test of:

a) a single crystal with [100] tensile axis


b) a single crystal with [110] tensile axis
c) polycrystal
Menu

莫泽民 CM MOK cmmok128@yahoo.com

Online reading materials:

Ductile Iron Tutorial


http://www.ductile.org/didata/Section2/2intro.htm
Alloys and Stainless Steels
http://www.roymech.co.uk/Useful_Tables/Matter/Alloy_Steels.html
Metallurgical Engineering
http://www.sut.ac.th/Engineering/Metal/course.html
Matters
http://www.matter.org.uk/steelmatter/metallurgy/default.htm

Appendix D. Page 116 of 116.

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