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Material
and Powder
Properties
Hgans Handbook for Sintered Components
Material
and powder
properties
Copyright Hgans AB
December 2013
0674HOG All rights reserved
Hgans Handbook for Sintered Components is intended for customer use.
The data presented in the handbook has been obtained from test specimens,
sintered under well-controlled conditions, in the Hgans AB laboratory.
Note that data established for any particular production equipment
or conditions may differ from those presented in this handbook.
All trademarks mentioned in this handbook are owned by Hgans AB,
Sweden and registered in all major industrial countries.
PM-SCHOOL HANDBOOK 1
Material and Powder Properties

1.
2.
3.
Material Science
Production of Iron and Steel Powders
Characteristics of Iron and Steel Powders
Production of Sintered Components

4.
5.
6.
7.
Compacting of Metal Powder

Compacting Tools
Sintering
Re-pressing, Coining and Sizing
Design and Mechanical Properties

8. Designing for P/M Processing
9. Sintered Iron-based Materials
10. Supplementary Operations
Material and powder properties

Material Science . . . . . . . . . . . . . . . . . . . . . .7
1.1 The Natural States of Matter . . . . . . . . . . . . . . . 8
1.2 The Crystalline Structure of Metals . . . . . . . . . . . . 10
1.3 Diffusion in Metals . . . . . . . . . . . . . . . . . . . . 26
1.4 Binary Phase Diagrams of Metals . . . . . . . . . . . . 33
1.5 The Iron-Carbon System . . . . . . . . . . . . . . . . . 46
1.6 Transformation Diagrams of Steels . . . . . . . . . . . . 58
1.7 Influence of the Microstructure on the Properties of Steel 67
Production of Iron and Steel Powders . . . . . . . . . 75

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . 76
2.2 The Hgans Sponge Iron Process . . . . . . . . . . . 78
2.3 The Hgans Water-Atomizing Process . . . . . . . . . 82
2.4 Hydrogen-reduced Iron Powder . . . . . . . . . . . . . 84
2.5 Alloying Methods . . . . . . . . . . . . . . . . . . . . . 85
2.6 Distaloy and Starmix . . . . . . . . . . . . . . . . . . 87
Characteristics of Iron and Steel Powders . . . . . . . 95

3.1 General Aspects . . . . . . . . . . . . . . . . . . . . . 96
3.2 Properties of Hgans Iron Powders . . . . . . . . . . 100
Index
108
This chapter presents a selection

of metallurgical concepts and
methods essential to the
understanding of basic processes
in powder metallurgy in
particular iron powder metallurgy.
The somewhat shorthanded
presentation of some items may
stimulate the reader to collect
further information from pertaining
special literature.
Material Science
1.1
1.2
1.3
1.4
1.5
1.6
1.7

The Natural States of Matter . . . . . . . . . . . . . . 8

The Crystalline Structure of Metals . . . . . . . . 10
Diffusion in Metals . . . . . . . . . . . . . . . . . . . . . . 26
Binary Phase Diagrams of Metals . . . . . . . . . 33
The Iron-Carbon System . . . . . . . . . . . . . . . . . 46
Transformation Diagrams of Steels . . . . . . . . 58
Influence of the Microstructure
on the Properties of Steel . . . . . . . . . . . . . . . . 67
MATERIAL SCIENCE
1.1 The Natural States of Matter

All matter surrounding us consists of atoms, ions and molecules, which,
depending on their mutual distances, are under the influence of stronger or
weaker reciprocal forces. Depending on the strength of their reciprocal forces,
these particles form gases, liquids or solids.
In gases. The particles (i.e. atoms, ions or molecules) move about highly
irregularly at very high speeds (some 100 m s-1 at Room Temperature). Their
free length of way, , (i.e. the distance a particle can move before colliding with
another one) is large compared to the particle diameter. Their density is in the
order of 1019/cm3. This situation is called random order. See Fig. 1.1 a.
In liquids. The particle density is in the order of 1022 / cm3. The particles move
about rather irregularly but are more crowded than in the gaseous state, each
particle having approximately ten very close neighbours. Significant for liquids
is the frequent local formation of crystal-like agglomerates extending over
several particle diameters. Because of the high thermal energy of the particles,
these agglomerates are very short-lived and there is no correlation between
more distant particles. This situation is called instable short-range order. See
Fig. 1.1b. In contrast to gases and liquids, amorphous and crystalline materials
exhibit, within a certain range of temperatures, a considerable rigidity they
are solids.
In amorphous solids. The particle density is of the same order of magnitude as
in liquids, i.e. 1022/cm3. Similar to liquids, a short-range order exists between
particles. But in contrast to liquids, due to the heavily restricted mobility of the
particles in amorphous solids, this order is stable and, logically, it is called stable
short-range order. See Fig. 1.1 c. Amorphous materials have no sharply defined
melting point. The transition from their solid to their liquid state occurs gradually.
They can, in fact, be looked at as liquids with an extremely high viscosity at
room-temperature. Classic examples are glasses. But today, by means of special
processes, also metals can be transformed into an amorphous state.
The Natural States of Matter
In crystalline solids, such as metals, the particle density is in the order of 1023 /cm3 ,
i.e. ten times higher than in liquids and amorphous materials. The particles
are homogeneously distributed and form a strict geometrical structure. See
Fig. 1.1d. Their mobility is restricted to very small vibrations around fixed
equilibrium sites. These vibrations increase with temperature. This situation is
called crystalline long-range order. The crystalline state possesses the lowest
internal energy of all states of matter and, therefore, is stable below a sharply
defined melting point. The above mentioned states are not specific to any
particular kind of material. In principle, but not always in practice, any type of
material can adopt any of these states.
a)
c)
b)
d)
Figure 1.1 Distribution of atoms in gases, liquids, amorphous and crystalline solids
(schematically);
a. Gas: statistical distribution, Number of atoms per cm3 = 1019, = free length of way.
b. Liquid: instable close-range order, Number of atoms per cm3 = 1022.
c. Amorphous solid: stable close-range order, Number of atoms per cm3 = 1022.
d. Crystal: crystalline order, Number of atoms per cm3 = 1023.
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MATERIAL SCIENCE
1.2 The Crystalline Structure

of Metals
Our further considerations are focused mainly on the crystalline in
particular the metallic state of matter. The formation of crystalline
structures is controlled by certain binding-forces between the atoms.
Geometrical descriptions of crystalline structures refer to so-called ideal
crystals only and do not take into account disturbances occurring in real
crystals, such as surfaces, grain-boundaries, dislocations, vacancies, foreign
atoms and other irregularities. In the following paragraph, we will discuss;
1) various types of bonding between atoms,
2) structures of ideal crystals,
3) stacking faults and disturbances in real metal crystals, and
4) plastic deformation in metal crystals.
1.2.1 Bonding Between Atoms
Crystal structures owe their existence to various types of interatomic forces

between neighbouring atoms. Four characteristic types are recognized: Van der
Waals, covalent, ionic and metallic.
Van der Waals force. This is the only appreciable force exerted between well
separated atoms and molecules. It is a weak attractive force that acts between all
atoms and is responsible e.g. for the condensation of noble gases and chemically
saturated molecules to liquids and solids at low temperatures. Its explanation
requires quantum mechanics because it involves fluctuations of the electronic
charge in the atom.
When two atoms approach fairly closely these fluctuations can occur in unison
so that one atom has its electrons slightly nearer the other nucleus whenever
this nucleus happens, through the movements of its own electrons, to be more
exposed in this direction than usual.
The Crystalline Structure of Metals
Ionic bond. Neighbouring atoms exchange electrons and the so formed positive
and negative ions are pulled together electrostatically as, for example, in
NaCl-crystals.
Covalent bond. Partly empty electron shells of neighbouring atoms overlap so
that their electrons belong to both atoms. This leads to strong bonds between
the atoms because in the overlapping shells their electrons are in a lower state
of energy than in separate shells. One important feature of these bonds is that
they can exist between atoms of the same type between which there can be no
ionic bonding. Examples are H2 ,O2 and Cl2. One other important feature of these
bonds is that they act in preferential directions as, for example, in the tetrahedral
structures of the CH4-molecule and of diamond.
Metallic bond. This type of bond can be explained only on the basis of the
following quantum-mechanical principle. All atoms in the metal crystal form
one common band of electron shells to which each individual atom contributes
one electron. These electrons, not being bonded to individual atoms, can move
freely inside the entire metal crystal. They form a so-called electron gas.
According to an obsolete electrostatic theory, the negatively charged electron
gas presses the negatively charged metal ions closely together. But the correct
explanation is that the mentioned arrangement constitutes the lowest possible
quantum state of energy for the metal crystal and allows the atoms to be packed
in the closest possible way. To this kind of close packing, metals owe their good
plastic formability. The freely moving electrons are responsible for the high
electrical and thermal conductivity of metals and for the characteristic metallic
gloss.
The overwhelming majority of all chemical elements crystallize in metal
structures, approximately one third of them each in BCC-, in FCC- and in
HCP-structure.
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MATERIAL SCIENCE
See Table 1.1. The geometrical characteristics of these particular structures are
described in the following paragraph.
Table 1.1. Crystal structures and lattice constants of some metals.*
Structure
Metal
BCC
-Fe
-Fe
1390
2,932
Mo
3,147
3,165
900
Ni
3,306
3,524
467
Cu
-Fe
Ratio of Lattice
Constants c/a
2,86
2,884
-Co
HCP
Lattice Constants
a) 10-10 m; c) 10-10m
Cr
-Ti
FCC
Temperature C
3,560
3,619
1000
3,651
Ir
3,839
Pt
3,923
Al
4,049
Au
4,078
Ag
4,086
Pb
4,950
-Co
2,506; 4,068
1,62
Zn
2,665; 4,947
1,86
-Ti
2,950; 4,679
1,59
Cd
2,979; 5,617
1,89
Mg
3,209; 5,210
1,62
(ideal)
* W. Schatt: Einfhrung in die Werkstoffwissenschaft. VEB Deutscher Verlag fr Grundstoffindustrie,

Leipzig 1981, S.55.
1,633
c
Figure 1.2. Unit cell in a crystal
cell; lattice constants: a, b, c.
1.2.2 Ideal Crystals
A crystal structure has three general properties: periodicity, directionality and

completeness.
Periodicity is the regular repetition in space of the atomic unit of the crystal
(wallpaper pattern). It is the basis of the remarkable plastic properties of
crystals. Directionality of the crystal structure appears in the fact that properties
like conductivity and elasticity vary with the direction of their measurement.
Completeness is simply the filling of all crystal sites defined by the periodic
structure with the required atoms.
In crystallography, it is customary to present a crystal structure graphically as
a space lattice within which the sites of atoms are marked by points (or small
circles). These points are referred to as lattice points. The basic unit of the crystal
structure which repeats itself in all three directions of space is called unit cell.
The defining edges of this cell are referred to as lattice constants, (usually a, b,
c). See Fig. 1.2.
The lattice points lie at the intersections of three families of parallel planes,
called lattice planes. The distance between neighbouring lattice planes is usually
designated by the triple-indexed symbol d h k l. See Fig. 1.3.
The spatial orientation of any lattice plane is clearly defined by its
so-called Miller indices (h k l), which are determined in the following way:
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MATERIAL SCIENCE
LP
LP
LP-family
LP
LP-distance
Figure 1.3. Lattice planes (LP)

in a crystal lattice.
LP-distance
LP
LP
LP
Choose a coordinate system with the origin at the corner of one unit
cell and with its axes parallel to the edges a, b, c of this unit cell.
Determine the intersections of the plane with the tree axes, x y z, of this
coordinate system.
Express, in units of a, b, c, the distances of these intersections from the
origin of the coordinate system: ma, nb, pc.
Take the reciprocals 1/m, 1/n, 1/p and find three natural numbers
related to one another in the same way as the reciprocals: 1/m : 1/n : 1/p
= h : k : l. Put the result between round brackets: (h k l).
Example: The plane, shown in Fig. 1.4, intersects the coordinate axes
at 2a, 4b and 1c respectively. The above procedure applied to this plane
yields m = 2, n = 4, p = 1. Thus, it follows: 1/2 : 1/4 : 1 = 2 : 1 : 4, and
the Miller indices of this plane are:
(h k l) = (214).
Figure 1.4. Derivation

of Miller indices.
Lattice planes and their Miller indices play an important roll e.g. in X-ray
structural analysis. Each family of planes is responsible for specific X-ray
reflections from which the respective Miller indices can be calculated and
conclusions can be drawn as to the type of crystal structure.
Some significant lattice planes of the cubic crystal system and their respective
Miller indices are shown schematically in Fig. 1.5.
Figure 1.5. Miller indices for some important lattice planes in cubic crystals.
Not only lattice planes but also lattice directions can be described by Miller
indices. A lattice direction is defined as the direction of a local vector
r = u a + v b + w c, originating from the corner of a unit cell, a, b, c being the
edge vectors of the cell (unit vectors of the coordinate system x, y, z).
The statement of the three coordinates of the vector in square brackets [uvw]
definitely identifies a given lattice direction. In the cubic system (and only
15
16
MATERIAL SCIENCE
there), a lattice direction [uvw] is always perpendicular to the lattice plane (hkl)
of same indices (h = u, k = v, l = w). The coordinates of the local vector r, put in
double square brackets [[uvw]], specify a lattice point. Some lattice directions
and lattice points are indicated in the schematic drawing in Fig. 1.6.
Figure 1.6. Lattice points and lattice

directions in the cubic crystal system.
For the characterization of lattice planes, directions and points in hexagonal

crystal systems, four instead of three Miller indices are required. Their detailed
description can be found in pertaining special literature and has no bearing on
our further discussions.
As already mentioned, all metals crystallize either in a body-centered-cubic
(BCC), in a face-centered-cubic (FCC) or in a hexagonal close-packed (HCP)
structure. The respective unit cells of these structures are shown in Fig. 1.7.
The dice-shaped unit cells of the BCC- and of the FCC-structure are each
presented in two different ways: to the left as abstract point lattice, and to the
right as conglomerate of spheres. The sphere-model conveys a fairly realistic
picture of the packing structure of the atoms inside the crystal.
BCC
r
ar = 4 r / 3
ar = 4 r / 2
NA = 2
NN = 8
PD = 68%
FCC
NA = 4
NN = 12
PD = 74%
HCP
NA = 6
NN = 12
PD = 74%
d= 2r
FCC
B
A
h = d 3
Figure 1.7. Unit cells of some important crystal structures: body-centered cubic (BCC); face
centered cubic (FCC); and hexagonal close-packed (HCP). NA = number of atoms/elementary
cell; NN = number of nearest neighbours; PD = packing density.
From the unit cells presented in Fig. 1.7, three significant parameters can
be derived, viz. the number of atoms per unit cell, NA, the number of nearest
neighbours, NN, and the packing density PD. The number of atoms, NA, is easily
obtained in the following way:
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MATERIAL SCIENCE
In the case of the BCC-cell, putting together an eighth of an atom from

each corner of the cell, and adding the one whole atom from the center
yields 2 whole atoms per unit cell: NA = 2.
In the case of the FCC-cell, putting together an eighth of an atom from
each corner of the cell, and putting together to 3 whole atoms the 6
halves of an atom from the faces of the cell, yields 4 whole atoms per
cell: NA=4.
In the case of the HCP-cell, putting together the 12 sixth of an atom
from the corners of the cell, putting together to 1 whole atom the two
halves of one atom from the hexagonal faces, and adding the three
atoms from inside the cell yields 6 atoms per cell: NA = 6.
Obviously, for the BCC-cell, the number of nearest neighbours is NN = 8. The
number of nearest neighbours for the FCC- and for the HCP-cell becomes evident
when looking at the plane of close-packed atoms (shaded), within which each
atom has 6 nearest neighbours. In addition, each atom has 3 nearest neighbours
each in the two planes above and beneath the shaded plane. All together, they
add up to 12 atoms: NN = 12.
Both, in the FCC- and in the HCP-structure, atoms are packed at maximal
possible density, viz. PD 74%. The packing density of the atoms in the BCCstructure is only PD 68%. The reader can easily verify these two figures by
dividing the volume of atoms belonging to one unit cell (NA/4 r3/3) with the
volume of this cell (a3 ).
In Fig. 1.7, for comparison, fully close-packed lattice planes in the HCP- and
in the FCC-structure are marked by shading. The diagram in Fig. 1.8 (a) shows
a fully close-packed plane. The spheres or atoms lie in three sets of close-packed
lines, physically equivalent and symmetrically orientated to one another. Both,
the HCP- and the FCC-crystal structure are formed by stacking a number of
close-packed planes on one another in a certain stacking sequence.
FCC
FCC
A
C
B
A
C
B
A
HCP
HCP
A
B
A
B
A
B
A
FCC-Twinn
FCC-Twinn
A
B
C
A
C
B
A
Figure 1.8. Arrangement of atoms in a close-packed plane (a), and in successive closepacked planes (b) and (c). Below: stacking sequences of close-packed planes in FCC and
HCP crystals.
The diagram in Fig. 1.8 (b) shows an element of the stacking sequence, a layer
B laid on a similar layer A in the most closely packed way. The layers have the
same orientation and each B atom rests symmetrically in a hollow provided by
three adjoining A atoms. We notice that only one-half of the hollows are used
by B atoms and that an equally close-packed arrangement would result if we had
used the other hollows, i.e. the C positions in diagram (c), instead.
Any stacking sequence chosen from the A, B and C positions is fully closepacked provided positions of the same type are not used by neighbouring planes.
For example, ABACBABAC is close-packed but ABBAAACCBBC is not.
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MATERIAL SCIENCE
The stacking sequence ABABAB forms the HCP-structure, and ACBACBACB

forms the FCC-structure. In FCC-structures, the stacking sequence occasionally
forms mirror images of itself like ABC(A)CBA(C)ABC.
This kind of stacking faults is called twinning. Crystal twins occur frequently
in copper, nickel and austenitic steels and appear on micrographs as parallel
stripes inside the crystal grains.
1.2.3 Real Metal Crystals
All metals used in technical applications (apart from single crystals and whiskers)
have a polycrystalline structure, i.e. they are composed of many randomly
oriented small crystal grains agglomerated to one another. When cooling down
a molten metal below its melting point, at first, very small dendrites (crystal
nuclei) precipitate from the melt. These dendrites gradually develop into small
crystallites which randomly oriented float around in the melt. Independently of
one another, the floating crystallites continue to grow, gradually depriving the
melt of atoms. Eventually, they get so crowded in the diminishing melt that they
begin to agglomerate. See Fig. 1.9.
Because of their original random orientation, a misfit between crystal lattices
occurs at the boundaries of adjoining crystallites (or crystal grains). In these
grain boundaries, atoms are not quite so closely packed as in the undisturbed
lattice inside the crystal grains. On a polished and etched metallographic section,
grain boundaries usually appear as thin dark lines.
Apart from grain boundaries, there are several other kinds of lattice
disturbances in real crystals. One distinguishes between zero-, one-, two-, and
three-dimensional lattice disturbances.
Figure 1.9. Formation of a polycrystalline
structure during solidification of a liquid
metal (schematically);
left: nucleation period (dendrites floating
in the melt);
right: end of solidification
( agglomerated crystallites).
2
1
Figure 1.10.
Zero-dimensional lattice
disturbances:
(1-1) vacancy,
(2-2) interstitial atom,

(3-3) bigger and,
(4-4) smaller substitutional
atoms.
Zero-dimensional lattice disturbances are

1) missing atoms in the regular lattice structure, (so-called vacancies),
2) foreign atoms occupying interstices between host atoms (interstitial atoms, and
3) larger or
4) smaller foreign atoms substituting atoms of the host lattice (substitutional atoms).
See Fig. 1.10.
One-dimensional lattice disturbances are so-called dislocations which occur

in two different varieties, edge dislocations and screw dislocations, forming
zones of lower packing-density which like filaments stretch through the crystal
structure. The schematic drawings in Fig. 1.11 shows one edge dislocation (a)
and one screw dislocation (b).
Figure 1.11. One-dimensional lattice disturbance: (a) edge dislocation, (b) screw dislocation;
in both cases, the dislocation line is perpendicular to the drawing plane.
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MATERIAL SCIENCE
Two-dimensional lattice disturbances are the above mentioned grain boundaries,

which can also be imagined as arrays of edge dislocations stacked on top of one
another.
See Fig. 1.12.
Figure 1.12. Two-dimensional lattice

disturbance: a grain boundary
(composed of an array of dislocation
lines stacked on top of each other) the
grain boundary face is perpendicular
to the drawing plane.
Three-dimensional lattice disturbances are non-metallic inclusions, dislocation

tangles, and small pores as occur in certain diffusion processes (Kirkendalleffect) and in sintering processes.
1.2.4 Plastic Deformation of Metal Crystals
Dislocations play the most essential part in plastic deformation of metals. Under
the influence of shearing-stresses, dislocations are created, and slip occurs on
certain lattice planes (mainly (111)-planes). On these slip planes, dislocation
lines move like waves along energetically favorable directions (mainly
[111]-directions).
This kind of slipping is facilitated by the circumstance that bonds between
adjacent atoms on both sides of the slip plane are not broken all at the same time
but successively one after the other. See Fig. 1.13.
Figure 1.13. Atomic bonds

transiently being ruptured
as dislocation travels
through crystal under
the influence of shearing
stresses.
Along a dislocation line perpendicular to the direction of slip, bonds are

temporarily suspended. As shown schematically in Fig. 1.14, the dislocation
line, driven by shearing-stresses, travels through the crystal achieving a small
displacement of the upper half of the crystal against its lower half.
Figure 1.14. Dislocation line, stretching from edge dislocation (a) to screw dislocation (b),
travels through a crystal, shifting its upper half relative to its lower half by atomic distance.
In order to achieve a noticeable plastic deformation, a great many dislocation

lines must travel through the metal. The more crowded the dislocations get, the
more do they interfere with one another: They get entangled, pile up against grain
boundaries (ends of slip planes) and catch on with inclusions and other lattice
disturbances. See Fig. 1.15.
The jamming and entangling dislocations build up a growing resistance
against further deformation which eventually ceases, unless shearing-stresses
are increased. This is the cause of the phenomenon of deformation hardening
and a contributing cause to dispersion hardening and other hardening processes.
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MATERIAL SCIENCE
When the temperature is raised, dislocations gradually dissemble as atoms escape

from them via vacancies. This dissembling mechanism is called dislocation
climbing.
Figure 1.15. Obstacles hampering the movement of dislocations; Top left: dislocations pile
up against grain boundaries (schematically); Top right: dislocation lines traveling from left to
right catch on with inclusions (schematically); Bottom: single dislocations (black lines) and
dislocation tangles (diffuse black spots) ina-iron with 0.91 at.-% Cu, plastically deformed by
4%, 50 000:1 replica.*
* E. Hornbogen, Symposium: Steel-Strengthening Mechanisms, Zurich, May 5th and 6th 1969.
See Fig. 1.16. Dissembling of jammed and entangled dislocations is the

mechanism behind the effect which soft-annealing has on cold-deformed metals.
The fact that metals deform easier at elevated temperatures is due the following
two processes:
1) the increased number and greater mobility of vacancies in the metal facilitate
the dissembling of dislocations, and
2) the thermal vibration of the atoms in their lattice sites is intensified. Both
processes have a lowering effect on the metals resistance to deformation, i.e.on
its yield point.
Figure 1.16. Dislocation climbing:

A dislocation dissembles gradually as
atoms escape from it via vacancies.
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MATERIAL SCIENCE
1.3 Diffusion in Metals

All processes and reactions taking place in gases, liquids or solids are depending
on the thermally activated exchanges of atomic particles controlled by laws
of thermodynamics and statistics. In homogeneous materials, the thermally
activated particles move around in all directions without any preference. When
gradients of temperature, pressure, concentration or electrical potential occur in
the material, the irregular movement of particles is superimposed by a drift in
the direction of the gradient (similar to a mosquito swarm drifting in the wind).
This drift of atomic particles is called (directional) diffusion. Diffusion usually
accomplishes a noticeable transport of material as, for instance, in the formation
or transformation of alloys and in the sintering of metal powders.
The movement and exchange of atoms in solid metals is feasible in various
ways. Inside the crystal lattice of the metal, small foreign atoms can move
relatively easily from interstice to interstice between the host atoms. This kind
of atom movement is called interstitial diffusion. See Fig. 1.17 (a).
The host atoms themselves and substitutional atoms can move only from one
vacancy to another. This kind of atom movement is called vacancy diffusion or,
pertaining to the host atoms, self-diffusion. See Fig. 1.17 (b). More easily than
in the close-packed lattice structure, atoms can diffuse along the less closely
packed grain boundaries and most easily along surfaces. Accordingly one speaks
of volume-diffusion, grain-boundary-diffusion and surface-diffusion.
Figure 1.17. Interstitial diffusion (a) and vacancy diffusion (b); (schematically).
Diffusion in Metals
1.3.1 Laws of Diffusion
In heterogeneous materials, concentration differences tend to level, because an

even distribution of concentration constitutes a state of minimal free enthalpy.
According to Ficks first law of diffusion, the number dn of atoms passing
through an area A perpendicular to the direction of their movement, during
a short time interval dt, is proportional to the concentration gradient -dc/dx
residing at the location of area A:
(1.1)
The proportionality factor D is called diffusion coefficient and is usually
measured in cm2 s-1. Equation (1.1) applies only if the concentration gradient
-dc/dx does not change during the whole diffusion process (stationary
case). Such is approximately the case, for instance, when carbon from a hot
carbonaceous gas diffuses through the thin steel wall of a furnace muffle. On
its inside, the muffle is being carburized by the carbonaceous gas, on its outside
decarburized by the surrounding air. As a consequence, a constant gradient of
carbon concentration establishes itself in the wall and carbon diffuses through
the muffle wall at constant rate.
If, in the course of diffusion, concentration changes everywhere in the material
(non-stationary case), Ficks second law of diffusion applies:
(1.2)
In cases where the diffusion coefficient D can be considered being independent
of the concentration c, this equation is simplified to:
(1.3)
Given the concentration distribution at the beginning of the diffusion process,
this partial differential equation can be solved by means of Gau error function
erf ( ). A relatively simple particular solution, applicable to many practical cases,
is presented in the following paragraph.
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MATERIAL SCIENCE
1.3.2 A Particular Solution of the Diffusion Equation
In many technical applications, the surfaces of two different metals are in such
intimate contact with one another that they can exchange atoms. Such is the case
e.g. when iron surfaces are protected with thin layers of zinc, copper, nickel or
chromium, or in powder metallurgy where powder particles of different metallic
identity are intimately pressed together in a compacting process.
In order not to confuse the understanding with complicated geometrical
parameters, we choose a solution of equation (1.3) applying to the simple
geometrical arrangement shown in Fig. 1.18: The end-faces of two oblong
metal bars, A and B, are closely pressed together. This simple model illustrates
the gradual leveling of concentration between two different metals which is
significant of all diffusion processes. The concentration distribution at the
beginning of the diffusion process is extreme, viz. 100% A-atoms in the left bar
and 100% B-atoms in the right bar. For this model, the particular solution of
equation (1.3) is:
(1.4)
where c (x,t) is the concentration of A-atoms in B at time t and distance x from
the contact surface between A and B. A large variety of numerical values of
Gau error-function erf ( ) can be found in relevant tables of mathematical
textbooks.
Diffusion in Metals
Figure 1.18. Course of diffusion between two bars of metals A and B (schematically).
Assumed are initial concentrations of 100% A-atoms in the left and 100% B-atoms in the
right bar. The curves are drawn according to equ. (1.4) and represent the distribution of
A-atoms across the two bars after different periods of time.
Remarkable with equation (1.4) is the circumstance that the concentration

c (x,t) does not depend explicitly of the individual parameters x and t but on
their combination as in the expression
. This means that any given
concentration of A-atoms in B moves in x-direction (i.e. from A to B) according
to the time law:
. This time law is significant of all diffusion processes
and controls e.g. the speed of growth of oxide layers on metal surfaces and the
travelling speed of a carburized zone from the surface to the center of a work
piece of steel.
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1.3.3 The Diffusion Coefficient
The diffusion coefficient D is a measure of the diffusion rate. D depends on

the mechanism of atom movement inside the metal and particularly strongly of
temperature according to the following relationship:
D = D0 exp ( Q / RT ) (1.5)
D0 is a characteristic property of the metal, R is the universal gas constant, T is
the absolute temperature, and Q is the activation energy.
D0 depends on the atomic weight of the diffusing atoms and on the melting
temperature of the metal in which diffusion takes place. In the case of vacancydiffusion, the activation energy is the sum of formation energy and migration
energy of vacancies. In the case of interstitial-diffusion, the activation energy is
identical with the traveling energy of interstitial atoms. The respective travelling
energies of atoms are lower in grain boundaries and lowest on surfaces.
Plotting the logarithm of D from equation (1.5) over 1/T , one obtains a straight
line with the slope Q/R. See Fig. 1.19. Thus, from the slope of this straight line,
the activation energy of the diffusion process can easily be calculated. Deviations
from the straight line indicate that several kinds of atomic movements with
varying activation energies are involved in the diffusion process.
Diffusion in Metals
Temp.
14
11
9 x 100 C
10 -10
Surface
D, m2/s (log-scale)
10 -12
Grain Boundary
10 -14
Volume
10 -16
-Fe
10 -18
9 x 10 -4
1/T (1/K)
Figure 1.19. Temperature dependence of the coefficients of self-diffusion of iron, for diffusion
along surfaces and grain boundaries and inside the crystal volume (In D over1/T).
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Diffusion coefficients D, material constants D0 and activation energies Q for

some important diffusion systems are presented in Table 1.2.
Table 1.2. Physical Data on some Important Diffusion Systems
Activation Energy Q
KJ/mol
kcal/mol
Diff.
Atom
HostCrystal
Fe
-Fe
(BCC)
2,0 x 10 -4
241
57,5
500
900
1,1 x 10-20
3,9 x 10-15
Fe
-Fe
(FCC)
5,0 x 10 -5
284
67,9
900
1100
1,1 x 10-17
7,8 x 10-16
-Fe
6,2 x 10 -7
80
19,2
500
900
2,3 x 10-12
1,6 x 10-10
-Fe
1,0 x 10 -5
136
32,4
900
1100
9,2 x 10-12
7,0 x 10-11
Cu
Cu
7,8 x 10 -5
211
50,4
500
4,4 x 10-19
Zn
Cu
3,4 x 10 -5
191
45,6
500
4,3 x 10-18
Al
Al
1,7 x 10 -4
142
34,0
500
4,1 x 10-14
Cu
Al
6,5 x 10 -5
135
32,3
500
4,8 x 10-14
Mg
Al
1,2 x 10 -4
131
31,2
500
1,8 x 10-13
Cu
Ni
2,7 x 10-5
255
61,0
500
1,5 x 10-22
D0 (m2/s)
T (C)
D (m2/s)
Binary Phase Diagrams of Metals
1.4 Binary Phase Diagrams

of Metals
1.4.1 Thermodynamics
First of all, some definitions are required:

A thermodynamic state is given through the following four parameters
of state: P, V, T and c (pressure, volume, temperature and concentration).
A heterogeneous system consist of several phases separated by
interfaces and having different properties (e.g. ice-crystals or droplets of
oil in Water).
A phase is in itself homogeneous and can consist of several
components present in varying concentrations (e.g. salt water consists
of H-atoms, O-atoms, Na-atoms and Cl-atoms).
Above-mentioned parameters of state given, number, type and relative amount
of different phases present in a heterogeneous system are stable, when the system
is in thermodynamic equilibrium. What is meant by this statement, will emerge
from the following consideration. A systems (e.g. a metals) internal energy E
is the sum of all individual kinetic and potential energies of its particles (metal
atoms). The external energy PV imposed on the system is the product of the
systems volume V and the external pressure P. The sum of these two energies
E + PV can also be split up according to a different aspect, namely into one part
which constitutes irreversible thermal energy TS (S = entropy) and another part
G which is available to accomplish work (e.g. transformation work). G is called
Gibbs free energy. This interrelationship is expressed by the following equation:
E + PV = TS + G (1.6)
Thus, Gibbs free energy is given by the expression:
G = E TS + PV (1.7)
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The expression:
F = E - TS (1.7a)
is called (Helmholtz) free energy. The differential of (1.7), constitutes the
change dG of free energy:
d G = d(E - ST + PV) = d F + d(PV) (1.8)

From the First and Second Law of Thermodynamics, in case T = constant and
P = constant:
dG = d(E ST + PV) 0 (1.9)

and, in case T = constant and V = constant, it follows:
dF = d(E TS) 0 (1.9a)
Since equilibrium reactions between metal phases usually take place at constant
pressure and constant temperature but sometimes are accompanied by volume
changes, equation (1.9) applies. This means that between phases striving for
equilibrium, only such reactions can take place that do not increase the free
energy, G. All reactions cease when the phases are in equilibrium and the
free energy, G has reached a minimum. The schematic diagram in Fig. 1.20
illustrates this situation.
Free Energy G
34
Solid
Liquid
Solid
Liquid
m.p
Figure 1.20. Change of free energy with temperature for a pure metal.
Temperature
The free energies of the liquid and of the solid state of a pure metal are plotted as
functions of temperature. The two respective curves cross at the metals melting
point. Below the melting point, the free energy of the solid state is lower than
the one of the liquid state. Above the melting point, the relation between the two
free energies is reversed.
1.4.2 Derivation of Binary Phase Diagrams
Applying the thermodynamic rules discussed in the preceding paragraph to a

heterogeneous system involving two components A and B and two phases 1
and 2, equilibrium, at given temperature and pressure, can be achieved only
by changing the concentrations of A and B in the two phases. The component
A will diffuse from phase 1 to phase 2, or vice versa, until the changes of free
energy with changing concentration are equal with respect to both phases, viz.:
(1.10)
The implication of this equation is that the two functions G1(c) and G2(c), plotted
in a G-c-diagram, have a common tangent when they are in equilibrium. On the
basis of these considerations, any binary diagram can be derived theoretically as
long as the respective free energies are known as functions of the concentration.
These functions can be deduced from the entropy of mixing of the involved
components. A discussion of entropy of mixing would exceed the frame of this
chapter, and is not required for the understanding of succeeding paragraphs.
Systems with Complete Miscibility in the

Solid and in the Liquid State.
For a metal system as defined in the heading to this paragraph, the free energies
GL(c) and GS(c) of the liquid and of the solid phase are plotted, as functions of
concentration and temperature, in a schematic diagram as shown in Fig. 1.21.
The melting point of the components A and B are denoted TMA and TMB (> TMA )
respectively. In the diagram, we distinguish between the following temperature
ranges:
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a) T > TMB
Over the entire range of concentration, the free energy curve GL(c) of the melt
lies below the free energy curve GS(c) of the solid. Over the entire range of
concentration, only the liquid phase is thermodynamically stable.
b) T = TMB
For c = 1 (100 %B), the free energy of the melt and the free energy of the solid
are equal: GL(c) = GS(c).
c) TMA < T< TMB
In this temperature range, the two free energy curves cross, and each curve
exhibits a minimum. The equilibrium of the two phases lies on the common
tangent of the two curves in accordance with equation (1.10). The abscissas of
the tangent points cL and cS correspond to the concentration of B in the melt and
in the solid phase respectively that are in thermodynamic equilibrium.
d) T < TMA
In this temperature range, over the whole range of concentrations, the free
energy curve of the solid lies below the free energy curve of the melt, viz. in
this temperature range, only the solid phase (composed of A- and B-atoms) is
thermodynamically stable.
Thus, the ranges of thermodynamic stability of the various phases in the binary
T-c-diagram (phase diagram) are separated by two theoretically deduced phase
borderlines (Liquidus and Solidus).
T>TMB
GS
GL
a)
Free Energy of Phases G(c)
T=TMB
GS
GL
b)
TMB>T>TMA
GS
GL
CL
c)
CS
TMA>T
GL
Figure 1.21. Deriving a binary phase
GS
diagram from the free energy curves

for the liquid and solid phases at
d)
different temperatures.
Temperature T
A and B are the components of the
TMB
Liquidus
system which are completely miscible

both in the liquid and solid state. GL
and GS are the free energies of the
liquid and of the solid state resp.
TMA and TMB are the melting points
Solidus
TMA
of A and B resp. CL and CS are the

concentrations of B in the liquid and
in the solid state resp.*
A
e)
Concentration c
* G.E.R. Schulze: Metallphysik, Akademie-Verlag, Berlin 1974.
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Experimentally, binary diagrams can be established by means of thermal analysis.

To this effect, from the two components of the system to be investigated, a number
of alloys of different composition are smelted and subsequently cooled. By means
of a thermocouple, the temperature changes during cooling are registered. On the
so-obtained curves, phase transformations show up in the form of kinks.
These kinks are caused by thermal energy being released during phase
transformation (lowering of free energy) and slowing down the rate of cooling. The
principle of this procedure is illustrated in Fig. 1.22. Typical representatives of this
simple binary system are the following pairs of metals: Cu-Ni, Ag-Au and Ag-Pd.
B
Li
Temperature T
Temperature T
38
So
A
a)
Time t

c3
c2
c1
Concentration c
b)
Figure 1.22. Experimental derivation of a phase diagram by means of thermal analysis, Left:
cooling curves for the two pure metals and for three of their alloys. Right: phase diagram
derived from cooling curves.*
Eutectic Systems.
More complicated phase diagrams can be derived theoretically and established

experimentally by methods analogous to the ones described above. As an
example, we will study the binary T-c-diagram of a so-called eutectic system as
presented in Fig. 1.23.
* W. Schatt: Einfhrung in die Werkstoffkunde, VEB Deutscher Verlag fr Grundstoffindustrie, Leipzig 1981.
In this system, two components (metals) A and B are completely miscible in the
liquid state but only to a limited degree in the solid state.
Temperature
Temperature
Figure 1.23. Experimental derivation of the phase diagram for a eutectic system of two
components A and B with limited miscibility in the solid state.
A remarkable feature of eutectic systems is the circumstance that at a certain

temperature TE (eutectic temperature) not two but three phases are in equilibrium
with one another, viz. a solid A-rich -phase, a solid B-rich -phase, and a
liquid phase L (the melt). The equilibrium relation between the three phases is
represented in the diagram by a horizontal tie-line (also called eutectic line) at
the level of TE. Above this line, there are two so-called 2-phase areas (+L) and
(+L) as well as one 1-phase area (L). All three areas join in one point E (the
eutectic point) on the eutectic line.
Below the eutectic line, there is one 2-phase area (+). To their left, the
2-phase areas border a single-phase area () and to their right, they border a
single-phase area (). In the (+L)-area, the melt is in equilibrium with the
solid -phase and in the (+L)-area with the solid -phase. In the (+)-area,
the two solid phases and are in equilibrium with one another. No additional
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MATERIAL SCIENCE
solid phases exist. To the right of the binary diagram, the cooling-curves for
three different alloys 1, 2, 3 are shown as obtained by thermal analysis. On the
cooling-curves for alloys 1 and 2, the eutectic reaction shows up in the form of
sharp kinks. Below the binary diagram, microstructures of the solidified alloys
are shown (schematically).
Alloy 1 of concentration cE (eutectic alloy) remains liquid until it passes the
eutectic line. Then, it spontaneously precipitates two different solid phases
and with concentration c and c respectively. The separation of the melt takes
place according to the eutectic reaction L + . The ratio of the relative
amounts of and in the microstructure of the solidified alloy is exactly equal
to the ratio of distance E - M2 and distance E - M1 on the eutectic line.
This relationship follows from a law called lever-rule of phases which will be
explained in paragraph 1.4.3.
Alloy 2 begins to solidify when passing the borderline between the melt (L)
and the (L+)-area. As temperature falls further, -crystallites of gradually
increasing A-concentration precipitate from the melt, depriving it of B-atoms,
according to the reaction L. As the alloy passes the eutectic line, the residual
melt spontaneously solidifies, precipitating -crystallites of concentration c
and -crystallites of concentration c, according to the eutectic reaction L+.
Also in this case, the above-mentioned lever-rule of phases applies.
Alloy 3 begins to solidify in a similar fashion as alloy 2, gradually reducing the
amount of the remaining melt. But on arrival at the borderline between the (L+)area and the ()-area, the residual melt has disappeared and the alloy is completely
solidified as -phase. On further cooling, the alloy passes the borderline between
the ()-area and the ( + )-area and is now tending to establish an equilibrium
between -phase and -phase according to the reaction + . Consequently,
-crystallites precipitate along the grain boundaries of the solid -structure.
Binary eutectic systems are formed e.g. by the following pairs of metals: Pb-Sn
(soldering alloys), and Cu-Ag (brazing alloys). In both cases, the eutectic allows
to make alloys that melt at considerably lower temperatures than any of the pure
metals they are composed of. Fig. 1.24 shows the binary system Pb-Sn and two
typical microstructures.
In the microstructure at left, the pre-eutectic Pb-rich -phase stands out as small
potato-shaped dark areas embedded in the subsequently formed eutectic. The
microstructure at right exhibits a plain eutectic with its typical arrangement of
alternating lamellae of - and -phase.
Pb Sn
327C
Liquid (L)
Temperature C
300
232C
+L
200
+L
187C
19,2
97,5
100
0
0
20
40
Pre-eutect (19,2% Sn)
Dark
(19,2% Sn)
60
80
100% Sn
Eutecticum (61,9% Sn)
Light
(97,5% Sn)
Figure 1.24. Phase diagram of the system Pb - Sn. Microstructures: -phase embedded in
eutectic (left) and pure eutectic (right).
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Peritectic Systems.
Concentration
Temperature
An equilibrium between three phases occurs also in a family of binary diagrams

called peritectic. In these systems, the melt reacts with an already precipitated
solid phase, say , in such a way that a different solid phase, say , is formed
according to the peritectic reaction L+.
Fig. 1.25 shows the binary diagram of a peritectic system and the cooling
curves by means of which it is established.
Temperature
42
Time
Figure 1.25. Experimental derivation of the phase diagram of a peritectic system A-B
Eutectoid Systems.
In some binary systems, as for instance in the iron-carbon-system, in addition

to the eutectic reaction between the melt and two solid phases L +, an
analogous reaction occurs between one solid phase and two other solid phases:
+ which is called eutectoid reaction.
The iron-carbon-system is of central interest not only to the metallurgy
of conventional steel but also to the powder metallurgy of iron. But before
concentrating on this important system, we want to give a more detailed
explanation of the above-mentioned lever-rule of phases and, in this context,
describe the phenomenon of crystal segregation which frequently occurs in the
solidification process of alloys.
1.4.3 The Lever-Rule of Phases
Guided by the simple binary diagram for two components A and B as shown in
Fig. 1.26, this rule is readily explained.
Liquid
TB
m0
mL
P0
mS
y
Figure 1.26. Lever-rule of phases;
mL = amount of residual melt with
concentration cL.
TA
mS = amount of solid phase with

concentration cS precipitated from
the melt.
Solid Solution
x = (c0 - cL) and y = (cS - c0),

c0 = initial concentration of the
melt = average concentration of
the solid alloy.
CL
C0
Concentration of B in A
CS
r-rule: mLy = mSx.
We assume that a given amount m0 of a molten alloy of concentration c0

(concentration of B-atoms) is rapidly cooled down to a temperature T0 inside
the 2-phase area (liquid + solid). Through P0 we draw a horizontal line (the
so-called tie-line) which cuts the two phase-borderlines at the points mL and mS
respectively. In this undercooled state, the melt of concentration c0 has become
thermodynamically instable.
According to the binary diagram, a melt of concentration cLshould now be in
equilibrium with a solid phase of concentration cS. In order to establish this new
equilibrium, crystallites of concentration cS > c0 must precipitate depriving the
melt of B-atoms. In this reaction, both, the total amount m0 = (mL + mS) of alloy
and the total amount c0m0 of B-atoms must remain unchanged.
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Thus, the following two laws apply:

(a) Conservation of total mass:
m0 = mL + mS
(b) Conservation of mass of B-atoms:
c0m0 = cLmL + cSmS
Inserting (a) into (b):
mL (c0 cL) = mS (cS - c0)
Evident from the diagram:
x = (c0 cL) and y = (cS c0)
Lever-rule of phases:
m0
mL
m S
c0m0
cLmL
cSmS
mLx = mS y
= mass of melt before solidification = total mass of alloy

= mass of residual melt after established equilibrium
= mass of solidified phase after established equilibrium
= mass of B-atoms before solidification
= mass of B-atoms in residual melt
= mass of B-atoms in solidified phase
The lever-rule of phases expressed in words: (amount of residual melt) x (tieline from balance point to liquidus line) = (amount of precipitated solid phase)
x (tie-line from balance point to solidus line).
1.4.4 Crystal Segregation
Frequently, during solidification of molten alloys, a characteristic phenomenon

called crystal segregation occurs, i.e. a heterogeneous distribution of concentration
inside individual crystal grains of the solidified alloy. Crystal segregation comes
about as follows:
As can be seen from the binary diagram shown in Fig. 1.27, solidification
starts with the precipitation of small B-rich dendrites of concentration c1 > c0. As
solidification continues, thin layers of decreasing concentration of B-atoms are
successively being deposited on the dendrites, wrapping them in onion skins
so to speak. In the outermost layer, the concentration of B-atoms is cn < c0. The
varying amount of B-atoms in the individual layers is a direct consequence of
the above-mentioned lever-rule of phases.
Although the concentration of B-atoms in the core of each crystal grain is higher,
and in its outermost zone lower, than the original concentration of the melt, the
average concentration of the alloy has not changed during solidification.
Concentration of A in B
Liquid
T1
Temperature
TB
C0
Tn
TA
Solid Solution
Figure 1.27. Crystal
Concentration of B in A
Cn
C0
C1
segregation;
c0= initial concentration
of the melt;
c1 = concentration of
dendritic crystal nuclei
first precipitated from
the melt;
cn = concentration of
residual melt solidifying
last.
When a molten alloy is cooled sufficiently slowly, due to diffusion processes,

concentration differences caused by crystal segregation level to a certain degree
already during continued cooling. In some cases, in order to improve the
properties of the solidified alloy, remaining concentration differences have to be
eliminated by means of a subsequent heat treatment called diffusion annealing
or homogenizing.
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1.5 The Iron-Carbon System
1.5.1 The Equilibrium Diagram: Iron-Carbon
This binary diagram applies to the equilibrium states of carbon-steel and castiron. The term carbon-steel refers to iron-carbon alloys containing less than
approximately 2% C. The term cast-iron refers to alloys containing between 2
and 4% C where the Fe-C-eutectic occurs. Of interest for technical applications
is mainly the iron-rich side of the diagram stretching to the concentration of the
inter-metallic phase Fe3C (6.67% C).
This part of the diagram is shown in Fig. 1.28 and can be looked at as being
composed of three sub-diagrams: one peritectic, one eutectic and one eutectoid
diagram. In connection with the heat treatment of steel, only the eutectoid subdiagram is of importance. The range up to temperatures of approx. 1150 C and
up to concentrations of approx. 1.5% C is of particular interest to the powder
metallurgy of iron.
Pure iron melts at 1536 C. Below this temperature, it solidifies in BCC crystal
structure, called -iron, which can dissolve max. 0.10% carbon interstitially (at
1493 C). On further cooling, at 1392 C, -iron transforms to FCC crystal
structure, called -iron, which can dissolve max. 2.06% carbon interstitially (at
1147 C). Carbon-containing -iron is called austenite. At 911 C, pure -iron
transforms again to a BCC structure, which is called -iron or ferrite, and which
is ferro-magnetic below 769 C (Curie-point). Ferrite can dissolve max. 0.02%
carbon (at 723 C).
Iron together with carbon forms the inter-metallic phase Fe3C, a carbide called
cementite, which has an ortho-rombic structure and a carbon content of 6.67%.
Cementite is a so-called meta-stable phase because, when annealed for long
times at high temperatures, it dissembles into iron and graphite.
Depending on whether carbon occurs bound in cementite or as free graphite,
one speaks of the meta-stable or of the stable system. Transformations in steel
and in white cast-iron proceed according to the meta-stable system (fully drawn
lines). Transformations in graphite-containing gray cast-iron proceed according
to the stable system C9D91.
An austenite containing less than 0.8% C transforms partly to ferrite when it
passes the phase-borderline GS (also called A3), and below the eutectoid line
PS (also called A1), its residue separates into ferrite and cementite, forming
The Iron-Carbon System
a lamellar structure called pearlite. An austenite containing exactly 0.8% C

transforms directly and entirely to pearlite when it passes through the eutectoid
point S.
An austenite containing more than 0.8% C transforms partly to cementite
(secondary cementite) when it passes the phase-borderline SE (also called Acm)
and below the eutectoid line SK, its residue transforms directly to pearlite.
Figure 1.28. Equilibrium phase diagram of the system Iron-carbon: fully drawn lines =
metastable system (Fe-Fe3C), broken lines = stable system (Fe-graphite).
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With reference to these three model cases, one distinguishes between

hypoeutectoid, eutectoid (pearlitic) and hypereutectoid iron-carbon-alloys or
steels. The respective microstructures are presented schematically below the
diagram. Real microstructures of austenite, ferrite, pearlite and cementite are
shown in Fig. 1.29.
Figure 1.29. Microstructure of steel; a. Austenite (stainless steel), b. Ferrite (< 0.02% C),
c. Ferrite + Pearlite (0.30% C), d. Pearlite + Ferrite (0.60% C), e. Pearlite (0.85% C),
f. Pearlite + grain boundary cementite.*
* Jrnets och stlets metallografi, Sandvikens Jernverks Aktiebolag 1964.
1.5.2 The Non-Equilibrium Diagram: Iron-Carbon
The iron-carbon diagram as shown in Fig. 1.28 like the binary diagrams treated
further above pertain to states of equilibrium and can, in principle at least, be
deduced theoretically from classical thermodynamics. With cooling rates as usually
practiced in the steel-producing and steel-working industry, states of equilibrium are
not always easily achievable and, in many cases not even desirable.
On the contrary, it is just the aimed provocation of certain meta-stable states that
offers outstanding technical advantages. With their corresponding microstructures,
the value scale of properties like tensile strength, elongation, hardness and
toughness can be largely extended. By varying the additional parameters time
and cooling-rate, iron-carbon-based materials can be optimally adapted to a great
variety of applications.
At the present state of development of thermodynamic theories, it is still not
possible to quantitatively describe the states of non-equilibrium as occurring
during forced cooling of steels. Therefore, empirically-experimentally established
transformation diagrams are still the only basis on which heat treatments of steel
can be intelligently planned.
Such transformation diagrams, known as TTT-diagrams (for Time, Temperature,
Transformation), exist today for all common types of steel and can be found in
brochures made available by the steel producers. In paragraph 1.6, these diagrams
will be discussed in detail.
Transformations in the solid state require rearrangement of atoms by diffusion and
in some cases also certain mechanisms of shearing the crystal lattice. Since diffusion
is a time- and temperature-dependent process, the attainment of equilibrium is
the more retarded the more the steel is undercooled. At sufficient degrees of
undercooling, meta-stable and instable crystal structures (and corresponding
microstructures) occur which considerably deviate from equilibrium structures.
With increasing cooling rate, the phase-borderlines in the equilibrium diagram:
iron-carbon (Fig. 1.28), are moving towards lower temperatures, particularly the
borderlines GSE (A3 and Acm) and PSK (A1) of the austenite area. The diagram
in Fig. 1.30 shows the displacement of the A3-point and the of the A1-point with
increasing cooling rate for a steel with 0.45% C. As can be seen from this diagram,
the A3-point moves faster towards lower temperatures than the A1-point.
As a consequence, with increasing cooling rate, the formation of pre-eutectoid
ferrite is more and more reduced and, eventually, entirely suppressed as A3 and
A1 join in a common A-point. At still higher cooling rates, Bainite (AB) and
Martensite (MS) are formed.
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Figure 1.30. Influence of cooling rate on the position of the transition points A3 and A1 for a
steel with 0.45% C.*
The influence of cooling rate on the displacement of A3 and the A1, as just
described for a steel with 0.45% C, applies analogously to the entire eutectoid
part of the iron-carbon diagram, i.e. to all plain carbon steels.
The diagram in Fig. 1.31 illustrates the situation. Pertaining cooling rates are
stated along the right ordinate of the diagram. With reference to cooling rates,
one distinguishes between the following five steps of undercooling:
Undercooling step 0 (equilibrium).
Equilibrium transformation at very low cooling rate.
Undercooling step I.
Already at a cooling rate of 1 Ks-1, a reduced formation of pre-eutectoid ferrite

in under-eutectoid steels and of pre-eutectoid cementite in over-eutectoid steels
becomes noticeable. At further increased cooling rate, the formation of preeutectoid ferrite is gradually hampered to such a degree that it occurs only in steels
of very low carbon contents. The austenite transforms to pearlite of increasingly
finer lamellar structure which, when just about resolvable by light-microscopic
methods, is called sorbite. In hypoeutectoid steels, the formation of pre-eutectoid
cementite is completely suppressed.
Undercooling step II.
An extremely fine-lamellar pearlite, called trostite, is formed. Its lamellar

structure is resolvable by means of electron-microscopic methods only. The
united undercooling steps I and II are also called pearlite step.
* W. Schatt: Einfhrung in die Werkstoffkunde, VEB Deutscher Verlag fr Grundstoffindustrie, Leipzig 1981.
Undercooling step III.
In this so-called bainite step (below approx. 450 C), the diffusion of iron atoms
has practically ceased and a formation of pearlite is no longer possible. Only
the interstitial carbon atoms can still diffuse in this temperature range. Already
before the FCC austenite lattice shears into the BCC ferrite lattice, cementite
begins to precipitate. The resulting microstructure consists of finely dispersed
cementite particles in a matrix of acicular ferrite. It is a kind of dispersionhardened ferrite, so to speak. The orientation of the ferrite needles is related to
the initial austenite lattice.
1000C
1 Ks-1
15 Ks-1
40 Ks-1
900
800
700
50
100
150
200
250
300
400
500
I Pearlite formation whith recalescence
Temperature
600
II Pearlite formation whithout recalescence
500
400
Ks-1
III Bainite formation
300
200
IV Martensite formation
100
0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
1,8 %
Carbon Content
Figure 1.31. Influence of cooling rate on the position of phase boundary lines in the
eutectoid part of the Fe- Fe3C - diagram.
Cooling rate
Equilibrium
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Undercooling step IV.
In this so-called martensite step, the undercooling of the austenite is so extreme

that the diffusion of carbon atoms has ceased and, hence, the formation of
cementite has become impossible. The FCC lattice of the extremely undercooled
austenite shears diffusionless into a tetragonally distorted (BCT) ferrite lattice.
Since the so formed ferrite is extremely supersaturated with carbon, high
internal stresses occur in its lattice. The tetragonal distortion of the lattice and
the internal stresses increase with increasing carbon content. See Fig. 1.32. This
is the cause of the high hardness of martensite.
Figure 1.32. Influence of carbon content on the axis lengths of the tetragonal martensite
lattice.*
* K. Honda and Z. Nihiyama.
1.5.3 Mechanisms of Austenite Transformation
To further the understanding of austenite transformations, it will be helpful

to discuss in more detail the various mechanisms of diffusion and structural
changes involved in the formation of ferrite, pearlite, bainite and martensite.
In between the close-packed iron atoms in the FCC lattice of austenite, there are two
types of interstices: the smaller tetrahedral and the larger octahedral interstices
as shown in the schematic diagrams in Fig. 1.33. Carbon atoms dissolved in
austenite occupy octahedral interstices only, where they cause the least possible
lattice distortions and internal stresses. To each unit cell of the austenite lattice
belong four octahedral interstices (one at its center and a quarter of one on each
of its twelve edges). Thus, in each unit cell, there are four positions available to
be filled by carbon atoms. Since also four iron atoms belong to each austenite
cell, the theoretically possible concentration of carbon atoms in austenite would
be 50 atomic-% compared to their maximal concentration of 9.51 atomic-% in
reality. This means that, even at maximal carbon concentration, most octahedral
interstices in the austenite lattice remain unfilled.
Figure 1.33.
Tetrahedral (a)
and octahedral (b)
interstices in the FCC
lattice of austenite.
= possible sites of
carbon atoms.
a
Ferrite Formation.
Pure -iron does not contain any carbon atoms at all. In hypoeutectoid steels
(< 0.8 weight-% = 3.7 at.-%), at best, only one out of seven unit cells of austenite
contains one carbon atom. Between 911C and 723C, because of the sparse
distribution of carbon atoms, parts of the FCC austenite lattice can easily shear
into the BCC ferrite lattice, while carbon atoms, not dissolvable in ferrite, get
enriched in the residual parts of the austenite. This shearing mechanism requires
a minimum of rearrangement of iron atoms in the respective crystal lattices,
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MATERIAL SCIENCE
as becomes evident from the schematic diagram in Fig. 1.34. In the drawing
representing two adjacent FCC cells, certain iron-atoms (filled circles) are
connected by tie-lines in such a way that they form a body-centered-tetragonal
(BCT) cell. It does not take much imagination to comprehend that a slight
stretching of its horizontal and/or slight upsetting of its vertical edges turns
this BCT cell into an ordinary BCC cell. The theoretically possible positions of
carbon atoms are indicated by small black spots on the edges of the cell. Since
the described shearing mechanism occurs almost instantly, one could say that,
on cooling, the FCC lattice of austenite snaps into the BCC lattice of ferrite
(or vice versa on heating).
Figure 1.34. Geometrical

interrelation between the
FCC lattice of austenite and
the BCC lattice of ferrite.
= possible sites of carbon
atoms.
Cementite Formation.
The maximal solubility of carbon in austenite is 2.06 wt.-% = 9.51 at.-% and
occurs at 1147C (eutectic temperature). This means that scarcely twenty
percent of all theoretically possible positions are filled with carbon atoms (i.e.
less than one carbon atom per austenite cells). A denser filling with carbon
atoms (supersaturation) would increase internal stresses in the austenite lattice
to such extent, that the corresponding increase in elastic energy would exceed
the formation energy of cementite.
Consequently in case of supersaturation with carbon, the austenite tends to
lower its free energy by transforming to cementite. The tendency increases with
increasing degree of undercooling. The concentration of carbon in cementite is
25 at.-%, i.e. at least close to three times higher than in austenite. Thus, in order
to form cementite, considerable amounts of carbon atoms must be adequately
displaced by diffusion.
Not enough with carbon diffusion, iron atoms too must be rearranged by
diffusion in order to enable the austenite to transform partly into cementite. Thus,
the formation of cementite depends not only on the austenites opportunity to
lower its free energy but also on the actual mobility of the carbon atoms (which
decreases with increasing degree of undercooling). At temperatures where the
mobility of carbon atoms in the austenite lattice has ceased, cementite cannot be
formed, and martensite occurs instead. See further down.
Pearlite Formation.
Below the eutectoid temperature (723C), austenite separates into cementite

and ferrite, thereby lowering the free energy of the alloy. Nucleated at the
austenite grain-boundaries, lamellas of cementite and ferrite grow side by side
gradually towards the center of the austenite grains as shown in the schematic
diagrams in Fig. 1.35. The lamellar structure occurs because the precipitating
cementite completely deprives its austenitic neighbourhood of carbon triggering
its transformation to ferrite. With increasing degrees of undercooling, i.e.
decreasing temperature, the diffusion rate of carbon decreases and consequently,
the lamellar structure of the pearlite becomes finer (and harder).
Figure 1.35. Nucleation of pearlite colonies at austenite grain boundaries (left) and growth of
pearlite lamellas in austenite grains (right).*
Martensite Formation.
Martensite formation is based on the same mechanism as ferrite formation.

The difference lies in the cooling rate. At low cooling rates, carbon atoms
have sufficient time to diffuse and form cementite before the lattice of
*A.H.Cottrell: An introduction to Metallurgy, Edward Arnold (Publishers), London 1968.
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MATERIAL SCIENCE
the remaining austenite shears into the ferrite lattice. At very high cooling
rates, as in quenching procedures, carbon atoms cannot move fast enough to
avoid getting trapped inside the spontaneously forming ferrite. Since ferrite,
under equilibrium conditions, cannot dissolve more than 0.02 wt.-% = 0.09
at.-% carbon, it is now extremely supersaturated with carbon, and its lattice
correspondingly (tetragonally) distorted (ref. Fig 1.32).
The high internal stresses arising from this distortion are the cause of the high
hardness of martensite. In microstructures, the tetragonally distorted ferrite, i.e.
martensite, appears in the form of relatively coarse needles oriented at certain
angles inherited from the initial austenite lattice.
The small areas in between the needles are remaining austenite. See micrograph
in Fig. 1.36 a. When annealing martensite at temperatures above MS, finely
dispersed cementite precipitates from the supersaturated ferrite. See micrograph
in Fig. 1.36 b. Thus, the high level of internal stresses in the tetragonal ferrite
lattice is reduced, and the brittleness of the martensite correspondingly lowered.
Figure 1.36. Acicular martensite (a) and tempered martensite with finely dispersed
cementite (b).*
Bainite formation.
Bainite is of great technical interest because it offers a very favourable combination

of hardness and toughness not easily attainable with martensite. According to
differences in cooling conditions, one distinguishes between two kinds of bainite:
upper bainite and lower bainite.
Upper bainite occurs at temperatures around 500 C where diffusion rates of
carbon are relatively higher. Lower bainite occurs at temperatures around
300C (but above MS) where diffusion rates of carbon are relatively lower.
* K.J. Irvine, Symposium: Steel-Strengthening Mechanisms, Zurich, May 5th and 6th 1969.
In the case of upper bainite, small parallel ferrite platelets, nucleated by shearing
processes, grow gradually inside the austenite. Moving ahead of the growing
ferrite platelets, carbon atoms accumulate in the remaining austenite which gets
increasingly more restricted. Eventually, the remaining austenite becomes so
restricted and so much enriched in carbon that it transforms to cementite jammed
between the ferrite platelets. See micrograph in Fig. 1.37a.
In the case of lower bainite, ferrite platelets form in much the same way as
in upper bainite but faster. At the same time, the diffusion rate of carbon has
dropped so much that carbon atoms cannot move fast enough to avoid getting
trapped inside the fast growing ferrite platelets. In this respect, the mechanism
of lower bainite formation is quite similar to the mechanism of martensite
formation.
But in the case of lower bainite, temperatures are high enough to initiate
precipitation of finely dispersed cementite particles inside the ferrite platelets
immediately after they have been formed. See microstructure in Fig. 1.37 b.
One could say that lower bainite is a kind of self-tempered martensite. Indeed,
comparing Fig. 1.36 b with Fig. 1.37 b, it can be seen that the microstructures of
lower bainite and tempered martensite have a certain resemblance.
Figure 1.37. Lower (a) and upper (b) bainite in a bainitic steel (0.87% C; 0.44% Mn; 0.17% Si;
0.21% Cr; 0.39% Ni).*
* I.J.Habraken and M.Economopoulos, Symposium: Transformation and Hardenability in Steels, Ann Arbor,
Michigan, USA 1958.
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1.6 Transformation Diagrams

of Steels
As briefly mentioned in paragraph 1.5.2, the goal of commercial heat treatment of steel is attaining optimal combinations of properties adaptable to a large
variety of applications. This can only be achieved by steering the formation of
adequate microstructures via strictly controlled cooling rates and holding times.
Adequate heat-treating procedures cannot be designed on the basis of equilibrium
diagrams. To this end, a particular kind of empirically established transformation
diagrams are required, usually called Time-Temperature-Transformation
diagrams, or TTT-diagrams for short. According to the procedure by which
they are established, one distinguishes between Isothermal Transformation
diagrams (ITT-diagrams) and Continuous Cooling Transformation diagrams
(CCT-diagrams).
Before going into details, a general feature of phase transformations must be
briefly explained. Phase transformations in metals (like any kind of phase
transformations) pass through two characteristic periods: a period of nucleation
and a period of growth. Nucleation is a process in which small nuclei of a new
phase precipitate at random from the mother-phase. Growth means that nuclei,
which incidentally exceed a critical minimum size, begin to grow on account of
the mother-phase, eventually replacing it entirely.
The growth rate of the new phase is proportional to the residue of
untransformed mother-phase, i.e. at the beginning, the new phase grows fast,
but as the amount of mother-phase shrinks, the growth rate of the new phase
slows down accordingly. This mechanism yields the characteristic s-shaped
transformation curve as shown schematically in Fig. 1.38.
Transformation Diagrams of Steels
Degree of Transformation
Nucleation
Growth
Time
Figure 1.38. Typical s-shaped course of isothermal transformation passing from a period of
nucleation to a period of growth.
1.6.1 ITT-Diagrams
In order to experimentally derive an ITT-diagram, a series of small specimens

of the steel to be investigated are austenitized at a temperature above A3. From
austenitizing temperature, the specimens are individually quenched to certain preselected temperatures, where they are held for various lengths of time. Subsequently
they are quenched to Room Temperature. On the so-treated specimens, the amount
of residual austenite is determined by means of quantitative metallographic
methods. Plotting the so-obtained amounts of residual austenite against respective
holding times, characteristic s-curves (of type as discussed above) emerge one for
each holding temperature. On each of these curves, three points of time are marked:
1) the point of beginning transformation (100% austenite),
2) the point where the amount of residual austenite has decreased to 50% (50%
transformation) and
3) the point where the amount of residual austenite has dropped to 10% or less
(90 - 100% transformation). Transferring these three points from each individual
S-curve to a temperature-time-diagram, as illustrated schematically in Fig. 1.39,
one obtains an ITT-diagram with three characteristic nose-shaped curves,
representing beginning, half-completion and end of austenite transformation
respectively.
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Figure 1.39. Empirically derived ITT-diagram for a hypoeutectoid carbon steel (right) and its
relation to the equilibrium phase diagram Fe-Fe3C (left). Austenitizing above A3.
A = austenite, F = ferrite, P = pearlite, B = bainite.*
The following details are noted:

At low degrees of undercooling, i.e. at temperatures close below A1,
rather long periods of time elapse before transformation begins (hours
or days). Transformation product: pearlite (P) and residual austenite
(A).
With increasing degrees of undercooling, transformation begins
correspondingly sooner. Transformation product: P + A.
At medium degrees of undercooling, i.e. at temperatures between
approx. 550 and 500 C, transformation begins almost instantly (after
less than 1 second). Transformation product: P + A.
With further increasing degrees of undercooling, the beginning of
transformation is delayed again ( up to approx. 20 seconds). Transformation product: A + B (bainite).
* Sandvikens Jernverks Aktiebolag: Stl - struktur och vrmebehandling, 1958.
At quenching to temperatures below approx. 280 C, large parts of

austenite transform instantly (without preceding period of nucleation)
into martensite (M). The lower the quenching temperature, the smaller is
the amount of residual austenite.
Transformation product: x% A + (100 - x)% M.
The nose of the transformation curves between 500 and 600 C is called
pearlite-nose because above its tip, austenite transforms to pearlite. The noseshape of the transformation curves has a simple explanation. Close below A1,
the diffusion rate of carbon is high, but, due to the low degree of undercooling,
the probability of cementite nucleation is very low. With increasing degrees of
undercooling, the probability of cementite nucleation increases accordingly, but
the diffusion rate of carbon decreases. As a result of these two counteracting
processes, transformation times adopt a minimum between low and high degrees
of undercooling.
Carbon steels with less than 0.25% C are not well suited for heat-treating
procedures aiming at the formation of martensite or bainite. Their pearlitenose lies too far left in the ITT-diagram and cannot be bypassed at technically
practical cooling rates.
A cooling curve just touching the pearlite-nose is called critical cooling curve.
When the carbon content is increased or when alloying elements like Cr, Ni, Mn,
Si, or W are added, the pearlite-nose is shifted toward the right in the diagram,
the critical cooling rate is correspondingly decreased, and the formation of
martensite and bainite facilitated.
Certain combinations of Cr-, Ni-, Mn-, and Mo-additions entail transformation
curves with two noses. Underneath the pearlite-nose a so-called bainite-nose
occurs as in the ITT-diagram shown in Fig. 1.40.
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C
800
Hardness - RC
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F
A
1400
A0 3
A0 1
13
700
1200
24
600
Temperature
62
500
400
31
1000
A+F
A+P
26
30
800
300
600
200
400
37
B
MS
M 90
M 90
44
50%
50
ITT DIAGRAM
100
200
1 min.
32
0.5 1 2 5 10
1 hour
10 2
10 3
1 day
10 4
10 5
62
10 6
Time - seconds
Figure 1.40. ITT-diagram with pronounced bainite-nose for a steel with 0.42% C;
0.68% Mn; and 0.93% Cr.*
When cooling a big work piece of steel from austenitizing temperature,

center and surface are cooling at different rates. Then, it may happen that the
cooling curve pertaining to the surface bypasses the pearlite-nose, while the
curve pertaining to the center passes through it. In such a case, a martensitic
microstructure occurs at the surface and a pearlitic-bainitic microstructure at the
center of the piece.
See schematic diagram in Fig. 1.41. An analogous problem arises, when a
heat of smaller pieces is cooled, because pieces located in the outer parts of the
heat are cooling faster than those buried deeper inside. This kind of problem is
avoided if the heat is quenched to a temperature somewhat above martensite
formation (MS) and held there until transformation is complete.
* Atlas of Isothermal Transformation Diagrams, US Steel, Pittsburgh, 1951.
Figure 1.41. Cooling curves for surface and center of a small (fully drawn lines) and of a big
(dotted lines) work piece (schematically).*
1.6.2 Heat Treatment of Steel based on ITT-Diagrams
The properties of steel can be improved considerably through special heat

treatments, i.e. certain sequences of heating, quenching and tempering.
Properties like strength, hardness, toughness and ductility, depend essentially,
if not entirely, on the microstructure of the steel. Heat-treating procedures must,
therefore, be especially designed to attain the required microstructures.
* Sandvikens Handbok, Del 7, Vol II, Sandvikens Jernverks Aktiebolag, 1964.
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For the design of reliable heat treatments, ITT-diagrams are indispensable.

Depending on the kind of application, one or the other of the following four
standard heat treatments are frequently applied:
a) Quenching and tempering.
b) Martempering.
c) Austempering (Bainitizing).
d) Isothermal soft-annealing.
The schematic ITT-diagrams shown in Fig. 1.42 illustrate these procedures
which, in detail, can be described as follows:
a) Quenching and tempering:
On quenching to temperatures well below the martensite temperature (MS), the
austenite transforms to a structure consisting of martensite and smaller amounts
of retained austenite. In this condition, the steel is extremely hard but also
extremely brittle. In order to reduce its brittleness and increase its toughness,
the steel is subsequently tempered at temperatures above MS. Due to temperature
differences between surface and core or between thinner and thicker sections of
the steel piece, cracks may arise on quenching. Hence, this type of heat treatment
is less suited for big work pieces or pieces of complicate shape.
b) Martempering:
In this heat treating process, the risk of crack formation in the steel is avoided.
The steel is quenched in a bath at a temperature slightly above MS and held in
the bath until the core of the piece reaches bath temperature. During this period,
the bath temperature falls gradually below MS, and the austenite transforms
uniformly into martensite, whereupon the steel is removed from the bath and
allowed to cool in air. Subsequently the steel is tempered to desired hardness.
c) Austempering:
In this heat treatment, the steel is quenched to a temperature below the bainitenose but above MS, at which temperature the austenite is transformed isothermally
to bainite. Subsequent tempering is not required, since, even without tempering,
bainite offers a favourable combination of hardness and toughness.
d) Isothermal annealing:
In many alloyed steels, there is a pronounced minimum in the ending line of
the ITT-diagram at relatively high temperatures. Assuming that a soft ferritic-
Temperature
Temperature
Temperature
Temperature
pearlitic structure is to be obtained, advantage may be taken of the timetemperature coordinates of this minimum to design a short annealing cycle. This
is accomplished by cooling the steel initially in the austenitic state as rapidly
as convenient to the temperature of the minimum and holding it approximately
at this temperature for the time required to transform the austenite completely.
Subsequently, the steel may be cooled as convenient.
Figure 1.42. Four standard procedures for the heat treatment of steels: a. Quenching and
Tempering; b. Martempering; c. Austempering; d. Isothermal Annealing.*
* Atlas of Isothermal Transformation Diagrams, US Steel, Pittsburgh, 1951.
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These examples have shown that ITT-diagrams are helpful guides in designing
adequate heat treating procedures. In industrial practice, heat treatments rarely
proceed under strictly isothermal conditions. In many cases, continuous cooling
procedures are even more practical. Thus, one might think that CCT-diagrams
would be more adequate. But the derivation of CCT-diagrams is a rather tedious
task, and would, even if feasible, rarely be warranted since a particular CCTdiagram exactly presents but one sample; samples from other heats, or even
from other locations of the same heat, are likely to have slightly different
CCT-diagrams.
Thus, when used with discrimination and with its limitations in mind, the
ITT-diagram is most useful in interpreting and correlating observed phenomena
on a rational basis, even though austenite transforms during continuous cooling
rather than at constant temperature.
Influence of the Microstructure on the Properties of Steel
1.7 Influence of the Microstructure

on the Properties of Steel
1.7.1 Pearlite and Spheroidite
In pearlitic structures, lamellas of soft ferrite alternate with lamellas of hard

cementite. Under the influence of shearing stresses, plastic deformation
occurs essentially only in the soft ferrite lamellas where dislocations can move
relatively easily. The thinner the ferrite lamellas are, the more restricted, by the
rigid cementite lamellas, is the mobility of the dislocations. This explains why
the ductility of pearlite increases and its hardness correspondingly decreases
with the thickness of its ferrite lamellas as shown in the diagram in Fig. 1.43.
By means of elongated soft-annealing, the cementite lamellas can be
spheroidized. In the so transformed pearlite, also called spheroidite, small
spherical cementite particles are embedded in a coherent ferrite matrix. See
microstructure in Fig. 1.44.
Spheroidite is the most ductile variety of pearlite because, in its coherent ferrite
matrix, dislocations can move more freely, restricted only to a lesser degree by
the spherical cementite inclusions.
Figure 1.43. Hardness of pearlite as a function
Figure 1.44. Spheroidized cementite
of the distance between its lamellas.
(spheroidite) in a carbon steel with 1.30% C.
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See diagrams in Fig. 1.45. In mixed structures of pearlite and ferrite, strength
and hardness increase with increasing proportion of cementite, while toughness
and ductility decrease. See diagram in Fig. 1.46.
Figure 1.45.
Figure 1.46.
Figure 1.45 Influence of carbon content on hardness (a) and ductility (b) for a plain carbon steel
having fine and coarse pearlitic as well as spheroiditic microstructures.*
Figure 1.46. Influence of carbon content on the mechanical properties of a plain carbon steel
having a fine pearlitic microstructure.**
* ** Metals Handbook, Vol.4, 9.Edition, ASM, 1981.

**
1.7.2 Martensite and Bainite
Martensite is the hardest and most brittle of all phases occurring in microstructures
of steel. It has virtually no ductility at all. Its hardness increases with increasing
carbon content - first faster (up to approx. 0.4% C) then slower, approaching
a maximum at approx. 1% C. The diagram in Fig. 1.47 shows the influence of
carbon content on the hardness of martensite and pearlite.
Martensite owes its high hardness not to the presence of cementite, as is the
case with pearlite, but to the high internal stresses caused by its supersaturation
with carbon. In its heavily distorted crystal lattice, the number of sliding systems
available for plastic deformation is extremely low.
Figure 1.47. Influence of carbon content on hardness for plain carbon martensitic and fine
pearlitic steels.*
Since austenite has a higher density than martensite, a noticeable volumeincrease occurs on quenching. Due to the accompanying shearing stresses, big
or intricately shaped work pieces may crack when quenched. This constitutes
a serious problem in the heat treatment of steels containing more than approx.
0.5% C.
* E.C.Bain: Functions of the Alloying Elements in Steel, AMS, 1939.
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In the quenched state, martensite is too hard, too brittle and too crack-sensitive for
most applications. Its brittleness can be reduced and its toughness considerably
increased through tempering at temperatures between 250 and 650C. Internal
stresses in the martensite lattice dissolve already at approx. 200 C. During
tempering, carbon atoms have sufficient time to diffuse and form cementite
which precipitates in the form of finely dispersed particles inside the martensite
needles (ref. Fig. 1.36 b). Tempered martensite has a certain resemblance to
lower bainite (ref. Fig. 1.37 b). The size of the precipitated cementite particles
in martensite increases with tempering time and temperature.
By means of varying these two parameters, the properties of hardened steel
can be optimally adapted to many different applications. The diagrams in Fig.
1.48 and Fig. 1.49 illustrate these possibilities.
71
19
190
18
180
17
170
16
160
15
150
8
7
6
5
70
re
120
ng
th
60
110
100
Contra
ction
50
400
300
200
100
th
90
80
70
60
40
30
50
40
30
20
10
St
80
ng
ile
500
ss
re
10
oint
90
St
11
130
ns
600
ct
12
ld P
dne
pa
13
Yie
140
Har
Im
14
Te
100
0
100
20
Elongation 5
10
Elongation 10
200
300
400
500
600
0
700
Tempering Temperature, C
Figure 1.48. Mechanical properties as functions of tempering temperature for a steel,

quenched from 850C in oil, and containing 0.30% C; 0.25% Si; 0.60% Mn; 0.30% Cr;
3.30% Ni and 0.25% Mo.*
* Sandvikens Handbok, Del 7, Vol II, Sandvikens Jernverks Aktiebolag, 1964.
Hardness, HB
200
Elongation and Contraction, %
20
Yield Point and Tensile Strength, kgf/mm2
Impact Strength, kgf/mm2
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MATERIAL SCIENCE
Figure 1.49.
Hardness as
a function of
tempering time
and temperature
for a waterquenched eutec
toid plain carbon
steel.*
Since the microstructure of bainite - similar to that of tempered martensite - is

composed of finely dispersed cementite particles in a ferritic matrix, bainitic
steels offer favourable combinations of hardness, strength and toughness.
The diagram in Fig. 1.50 shows the influence of transformation temperature on
microstructure and tensile strength of a low-carbon bainitic steel.
Figure 1.50. Relationship between

temperature of maximum
transformation rate and strength
of low carbon bainitic steels.**
* E.C.Bain: Functions of the Alloying Elements in Steel, AMS, 1939.

** K.J. Irvine, Symposium: Steel-Strengthening Mechanisms, Zurich, May 5th and 6th 1969.
1.7.3 Temper Brittleness
With some types of steel, tempering may cause a marked decrease of impact
strength. This phenomenon, which is called temper brittleness, occurs either
when the steel is tempered above 575 C and subsequently slow-cooled to R.T.,
or when tempered between 375 and 575 C. Steels containing Mn, Cr or Ni and,
in addition, small amounts of impurities, like Sb, P, As or Sn, are especially
sensitive to temper brittleness.
When the mentioned alloying elements and impurities are present, the border
between tough and brittle tempered martensite is shifted noticeably to higher
temperatures. Crack propagation in temper-brittle steel proceeds along former
austenite grain boundaries where the impurities preferrably have segregated
during solidification of the melt. Temper brittleness can be avoided by reducing
the amount of impurities or by tempering above 575 C or below 375 C with
subsequent quenching to R.T.
73
This chapter presents a short

history of iron powder and a brief
account of how world production
and consumption of iron powder
have developed over the last four
decades. It describes in detail two
production methods which
together account for more than
90% of todays world production of
iron and steel powders.
Production of Iron
and Steel Powders
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 The Hgans Sponge Iron Process . . . . . . . . . .
2.3 The Hgans Water-Atomizing Process . . . . . .
2.4 Hydrogen-reduced Iron Powder . . . . . . . . . . . . .
2.5 Alloying Methods . . . . . . . . . . . . . . . . . . . . . . . . .
2.6 Distaloy and Starmix . . . . . . . . . . . . . . . . . . . .
76
78
82
84
85
87
76
PRODUCTION OF IRON AND STEEL POWDERS
2.1 Introduction
Iron and steel powders for the manufacturing of sintered structural components
(including sintered porous bushings) are produced in many parts of the world. The
worldwide consumption of such powders has been growing increasingly fast over
the last four decades and reached 900,000 metric tons by the end of 2010.
Over the last forty years, the quality of iron and steel powders has been
continuously improved and the spectrum of available grades has been widened.
During the same period, compacting- and sintering-techniques have become
more and more sophisticated. This development has lead to a substantially
widened range of applications for sintered and iron steel parts.
Table 2.1. Global Sales of all Iron Powders
Year
Tons of powder
1991
450
1992
475
1993
500
1994
565
1995
590
1996
600
1997
650
1998
670
1999
725
2000
775
2001
715
2002
785
2003
820
2004
890
2005
855
2006
895
2007
930
2008
850
2009
680
2010
945
Introduction
Table 2.1 shows that the worldwide sales of iron powders have more than
doubled over the last 20 years. It must be mentioned that, at present (2011), the
worldwide production capacity of iron and steel powders is considerably larger
than the consumption. Thus, there is no risk of shortage for many years to come.
Currently, there are two basically different production methods which together
account for more than 90% of the world production of iron and steel powders,
viz. the Hgans sponge-iron process and the water-atomizing process. The
former process is based on reduction of iron ore, yielding a highly porous
sponge-iron which subsequently is comminuted to powder. The latter process
is based on atomization of a stream of liquid iron (or steel) by means of a jet of
pressurized water. Both processes will be described in detail further below.
In the manufacturing of sintered parts, iron powders are always used admixed
with a small amount of lubricant in powder form in order to minimize the friction
in the compacting tool. In many cases, they are also blended with alloying
elements in powder form, like graphite, copper, nickel, molybdenum and others
(in order to achieve increased strength properties).
Since powder blends tend to segregate when transported and handled, Hgans
has developed special blending processes in which the alloying additives are
safely bound to the iron powder particles. Powder mixes produced according
to these processes are known as the trade names Distaloy and Starmix. These
two processes are treated in detail further below.
77
78
2.2 The Hgans Sponge

Iron Process
The Hgans sponge iron process, is essentially a chemical process in which
finely divided iron ore is being reduced with coke breeze yielding a spongy mass
of solid metallic iron, which can readily be comminuted to iron powder. The
iron ore used at Hgans is a magnetite (powder Fe3O4) obtained from selected
sources. This magnetite, which by nature contains only very small amounts of
gang and has extremely low contents of sulfur and phosphorus, is being dressed
and concentrated while still at the mining location and then delivered to Hgans
in a highly pure state.
As shown in the flow-sheet in Fig. 2.1, the process of transforming the magnetite
to iron powder proceeds as described on the next page.
The Hgans Sponge Iron Process
1. Reduction Mix of Coke Breeze and

Limestone
2. Iron Ore
3. Drying
4. Crushing
5. Screening
6. Magnetic Separation
7. Charging in Ceramic Tubes
8. Reduction in Tunnel Kilns,
Approximately 1200C
9. Discharging
10. Coarse Crushing

11. Storage in Silos
12. Chrusing
14. Grinding and Screening
15. Annealing in Belt Furnace,

Approximately 800-900 C
16. Equalising
17. Automatic Packing
18. Iron Ore
19. Reduction Mix
Figure 2.1. Flow-sheet for the Hgans Sponge Iron Process.
79
80
The process starts with two raw materials: a reduction mix consisting of
coke breeze blended with ground limestone (1), and a pre-processed iron ore (2).
The iron ore and the reduction mix are being dried separately in two rotary
dryers (3). The slightly agglomerated dried reduction mix is crushed (4) and
screened (5), and the dried iron ore is passed through a magnetic separator (6).
Then, both materials are charged by means of an automatic charging device
into tube-like ceramic retorts as illustrated (7), (18), (19). These retorts have
an Inner Diameter of 40 cm, are 2 m long, and consist of four tube segments
of silicon carbide being stacked on top of each other.
These retorts are standing, 25 each, on rail-bounded cars which are clad with a
thick layer of refractory bricks. These cars are traveling slowly through a tunnel
kiln of approx. 260 m length (8) within which the retorts are gradually heated
to a maximum temperature of approx. 1200C. As the temperature inside the
retorts increases, the coke breeze begins to burn forming CO which, in turn,
begins to reduce the magnetite to metallic iron while itself oxidizing to CO2.
The so generated CO2 reacts with the remaining coke breeze forming new
CO, which again reduces more magnetite to metallic iron. This reaction cycle
continues until all magnetite has been reduced to metallic iron and the major part
of coke breeze is burned up. Parallel to the reduction cycle, the limestone in the
reduction mix binds the sulfur arising from the burning coke breeze.
After completed reduction, the retorts are slowly cooled down again to approx.
250C before leaving the kiln. Inside each retort, there is now a tube-like sponge
iron cake with a porosity of about 75%, a residue of unburned coke breeze, and
a sulfur-rich ash. At an automatic discharging station (9), the sponge iron tubes
are pulled out off and the remaining coke breeze and ash are exhausted from the
retorts. Thereafter, the retorts are ready to be charged again and go on a new trip
through the tunnel kiln.
The sponge iron tubes (after having been cleaned from adhering coke breeze
and ash) are in several steps crushed and comminuted to a particle size below
3 mm (10). The so obtained crude powder is intermediately ensilaged before
further processing. From the intermediate silo (11), the crude powder is passed
through a specially designed chain of magnetic separators (12), mills (13) and
screens (14), in order to be refined to a particle size below 150 m (<100 Tylermesh) and a well defined bulk density (apparent density).
The Hgans Sponge Iron Process
Subsequently, the powder is passing a belt furnace (15) where it is soft-annealed

at 800 - 1000C in hydrogen, and its remaining contents of carbon and oxygen
are reduced to a very low level. During annealing, the powder agglomerates to
a very crumbly cake which is gently comminuted again in a special mill (not
shown on the flow-sheet). The so treated powder has good compressibility and
high green strength.
Many belt furnaces are, of course, available to take care of the huge volume
of iron powder to be treated.
The powder from the belt furnaces is collected and homogenized (16) in lots of
60 or 120 tons. Each lot is carefully checked with respect to specified properties
and packed (Fig. 2.2) and stored, ready for shipment (17).
Figure 2.2. Hgans standard packing, flexbag 1000 kg.
81
82
2.3 The Hgans Water-Atomizing

Process
A modern atomizing plant of Hgans AB is located at Halmstad, a small coastal
town 80 km north of Hgans. The water-atomizing process, as practiced there,
can be followed on the flow-sheet shown in Fig. 2.3, and is described in detail
on the next page.
1. Selected scrap
2. Arc furnace
3. Liquid Steel
4. Injection
5. Atomizing (see below)
6. Dewatering
7. Drying
9. Screening
10. Equalizing
11. Transportation
5. ATOMIZING
A. Tundish
B. Steel Stream
C. High Pressure Water
D. Nozzle
E. Atomized Iron Powder
Figure 2.3. Flow-sheet for the Hgans Water-Atomizing Process.
The Hgans Water-Atomizing Process
The raw material for this process is carefully selected iron scrap and sponge iron
from the process described in the preceding paragraph. This raw material (1) is
melted down in an electric arc furnace of 50 tons capacity (2) where, if desired,
alloying elements can be added.
The melt is teemed slag-free through a bottom hole into a ladle (3) where it is
refined with an oxygen lance (4). The ladle is then transferred to a ladle furnace
and on to the atomizing station (5), where the liquid iron (or steel) is teemed
slag-free through a bottom hole in the ladle into a specially designed tundish (A).
From there, the liquid iron (or steel) flows in a well controlled stream (B)
through the center of a ring-shaped nozzle (D) where it is hit by jets of highly
pressurized water (C). The stream of liquid iron (or steel) explodes into fine
droplets (E). Some of these droplets freeze immediately to small spheres, others
unite in small irregularly shaped agglomerates while freezing.
Air, swept along by the water jet, and water vapor arising in the atomizing
process, cause superficial oxidation of the small droplets. The solidified droplets
and the atomizing water are collected in a huge container, where they are settling
as a mud. This powder mud is de-watered (6) and dried (7).
The dry powder is magnetically separated from slag particles (8), screened (9)
and homogenized (10), and eventually transported in special containers (11) to
the works at Hgans for further processing.
In the state leaving the atomizing plant, the atomized powder particles are not
only superficially oxidized but also very hard because, due to the extremely
high cooling rates residing in the atomizing process, they have solidified in the
martensitic state despite their low carbon content.
The powder is, therefore, soft-annealed, and its surface oxides and residual
carbon are reduced in belt furnaces of the same type as described in the preceding
paragraph. Routines for homogenizing, quality checking, packaging and storing
are the same as for sponge iron powders.
83
84
2.4 Hydrogen-reduced Iron Powder

Hydrogen-reduced iron powder is manufactured from selected iron oxides
(Fe203) and is widely used for low density structural parts and bearings as well
as sintered friction materials. The powder particles are markedly irregular in
shape with a sponge-like microstructure. The irregular particle shape creates
very good mechanical interlocking which results in very high green strength.
The sponge-like particle structure provides a high surface area that promotes
sintering, resulting in increased shrinkage. Therefore, the hydrogen-reduced iron
powders provide high green strength, introduce porosity with fine pores while
maintain good strength as well as provide an alternative method for controlling
the dimensions of parts.
Figure 2.4 Flow-sheet for the Hydrogen-reduced Iron Powder.
Figure 2.5 Irregular particle shape of

hydrogen-reduced iron powder.
Alloying Methods
2.5 Alloying Methods

In order to achieve hardenable sintered ferrous materials, carbon and other
suitable alloying elements, like e.g. copper, nickel, and molybdenum, have to be
introduced. While carbon is normally admixed to the iron powder in the form of
graphite, metallic alloying elements are commonly introduced by either of the
following two methods:
Method 1: Water atomization of the liquid iron alloy, resulting in a
homogeneously alloyed powder.
Method 2: Mechanically blending plain iron powder with the
respective alloying elements in powder form, and letting the
actual alloying process take place during sintering of the parts
compacted from the powder mix.
Both methods have their advantages and disadvantages:
Homogeneously alloyed powders.
Advantages:
Alloying elements do not segregate when the powder is handled .
Yield fully homogeneously alloyed sintered parts.
Disadvantages:
Have low compressibility, because their particles are solutionhardened. (See Figs. 2.6 and 2.7).
In order to change or correct the composition of a fully alloyed powder,
if ever so little, a new melt (usually 50 tons at time) will have to be
atomized.
85
86
Powder mixes.
Advantages:
Have higher compressibility. (See Fig. 2.8).
No additional mixing operation is required as the powder has to be
admixed with a lubricant anyway.
The composition of a powder mix can very easily be changed or
corrected by re-mixing it with additional amounts of either iron powder
or alloying elements.
Disadvantages:
Yield less homogeneously alloyed sintered parts, because the admixed
alloying elements (except carbon) diffuse very slowly in solid iron.
(ref. Chapter 6, Figs. 6.9 and 6.10).
Alloying elements tend to segregate when the powder mix is transported and handled. (However, powder mixes can be made segregationresistant by means of special treatments as described in the following
paragraph).
The diagram in Fig. 2.6 shows the influence of alloying elements on the hardness
of iron.
Figure 2.6. Influence of some alloying elements on the hardness of iron.
DISTALOY AND STARMIX
2.6 Distaloy and Starmix

In order to eliminate the segregation problem with powder mixes, Hganshas
developed two special processes for the production of segregation-resistant
iron powder mixes. A large variety of standard and tailor-made powder mixes
produced according to these processes are offered under the trade-names
Distaloy and Starmix.
The Distaloy process can be described as follows:
Alloying elements used in the Distaloy process are mainly copper, nickel and
molybdenum (but not graphite!) in the form of very finely grained powders.
The process starts with weighing-in a production lot of 30 tons of iron powder
and alloying powders in exactly controlled proportions. This lot is mixed in a
double-cone mixer. Special precautions are taken to prevent segregation of the
mix when discharged from the mixer.
The so produced powder mix is heat-treated in a continuous furnace under a
reducing atmosphere at a temperature somewhat below the melting point of the
lowest-melting alloying element. During this heat-treatment, the fine particles
of the added alloying elements are safely bonded to the surfaces of the coarser
iron powder particles.
87
88
See SEM-photographs in Fig. 2.7. Due to inter-diffusion between the diffusion

bonded alloying particles and the iron particles, the latter become, to a certain
extend, locally pre-alloyed.
Figure 2.7. SEM-photographs showing fine particles of copper, nickel and molybdenum
diffusion bonded in the Distaloy process, to the surface of an iron powder particle.
The so treated powder mix contains the alloying additives as finely and evenly
dispersed as possible . The fact that the iron powder particles are locally prealloyed has practically no negative effect on the compressibility of the mix.
See Fig. 2.8, where the compressibility curve for a Distaloy grade is shown
in comparison with those for an ordinary powder mix and for an atomized
homogeneously alloyed powder of identical compositions.
Figure 2.8. Compressibility curves for three ferrous powders produced by different methods
but having the same chemical composition: 1.75% Ni, 1.5% Cu, 0.5% Mo, remainder Fe.
Graphite and lubricants have to be excluded from the Distaloy process because,
during heat-treatment of the powder mix, graphite would carburize the iron
particles and spoil the compressibility of the powder mix, and lubricants would
burn-off.
89
90
The Starmix processes uses special types of binders to glue graphite

and lubricants to the iron powder particles during the mixing procedure.
See SEM-photograph in Fig. 2.9.
Figure 2.9. SEM-photograph showing fine graphite particles glued, in the Starmix process,
to the surface of an iron powder particle (NC100.24).
Loss of Graphite, %
The Starmix processes can, of course, be applied to ordinary iron powder mixes
as well as to Distaloy powders; in both cases, it yields segregation-resistant
press-ready powder mixes. The gain in product consistency achieved through
the Starmix 500 process is illustrated in the diagrams in Figs. 2.10 to 2.13.
Conventional
mix
Starmix 500
Figure 2.10. Graphite loss in air de-dusting test for a Starmix treated powder mix
Frequency, %
and for a conventional powder mix.
Conventional mix
Starmix 500
Figure 2.11. Relative frequency of dimensional changes during sintering for

a Starmix treated powder mix and for a conventional powder mix.
91
Combined carbon, %
92
Figure 2.12. Variation
Starmix 500
1.20
of carbon content in
sintered parts during
1.10
mass production,
comparing Starmix
1.00
treated mixes and
Conventional mix
0.90
conventional mixes of
NC100.24 + 1.2%
5000
10000
15000
graphite.
Number of parts
Apparent Density, g/cm3

2.80
2.75
2.70
32
30
28
26
24
Green Density, g/cm3
Flow, sec/50 g
Green Strength, N/mm2
6.70
13
6.60
12
Tensile Strength, N/mm2
Elongation, %
400
4.0
Figure 2.13.
390
3.0
Comparison of powder
380
2.0
properties and sintered

properties for Starmix
Hardness, HV10
Dimensional Charge, %
140
+0.20
130
+0.10
treated mixes and

conventional powder
mixes of NC100.24 +
0.8% graphite + 0.8%
Zn-stearate.
Conventional mix
Starmix 500
Our Starmix Grades

Starmix 500
This is the standard Starmix for improved tolerances.

Better control of additives such as carbon crucial for heat-treated
parts
For improved tolerances in less demanding applications
Starmix 400
Starmix 400 has tailored properties for tolerance control in more complex parts.
Key properties can be fine-tuned to meet specific requirements
Improved performance in more demanding applications
Starmix 820
This Starmix provides tighter tolerances in components with high graphite

contents.
Delivers properties particularly suitable for valve guide applications
Starmix BOOST
Starmix BOOST is designed for parts with highly complex shapes.

Can be tailored for very demanding applications to meet tough
requirements on productivity, consistency and part precision
Excellent lubrication and high AD
New lubrication system without Zinc ensures a stain-free finished
component
93
The most important prerequisite

of a successful mass production of
high-quality sintered parts is a
high and consistent quality of the
powder from which the parts are to
be made. The characteristics of the
powder decide its compacting and
sintering behavior and, eventually,
about the properties of the finished
product.
Characteristics
of Iron and
Steel Powders
3.1
3.2
General Aspects . . . . . . . . . . . . . . . . . . . . . . . . . 96
Properties of Hgans Iron Powders . . . . . . . 100
96
CHARACTERISTICS OF IRON AND STEEL POWDERS
3.1 General Aspects

Iron and steel powders - as well as other metal powders - used in the production
of sintered parts can be characterized by three categories of properties:
1. Metallurgical properties
chemical composition and impurities

microstructure
microhardness
2. Geometrical properties
particle size distribution

external particle shape
internal particle structure (particle porosity)
3. Mechanical and physical properties
flow rate
bulk density
compressibility, green strength and spring back
All these powder properties are inherited from and specific to the process by
which the powder was produced. Some of them are interrelated with each other.
For instance:
microstructure and microhardness are depending on chemical
composition;
compressibility decreases with increasing microhardness,
increasing particle porosity and decreasing particle size;
coarser powders and powders of regular particle shape flow better
than fine powders and powders of irregular particle shape;
powders of irregular particle shape have better green strength after
compacting than powders of regular particle shape.
In the following, we present a brief definition of the aforementioned powder
properties and their relevance to processing steps in the production of sintered
parts.
General Aspects
Metallurgical Properties
are determined by chemical analysis and metallographic procedures. The chemical composition of a ferrous powder has a great influence upon the final strength
properties of the sintered parts. Non-metallic impurities may have an adverse
effect upon compressibility and upon the life of compacting tools.
Geometrical Properties
viz. particle size distribution, particle shape and particle porosity, determine the
powders specific surface which is the driving force of the sintering process
(Chapter 6).
Particle Size Distribution
is determined by sieve analysis or laser diffraction if particle sizes are above 45

m (minimum screen aperture). Finer powders are analyzed by means of laser
diffraction methods.
External Particle Shape
is analyzed by means of scanning electron microscopy (SEM). (See Fig. 3.1 left).
Internal Particle Structure
is analyzed by means of metallographic techniques. (See Fig. 3.1 right).
Figure 3.1. External particle shape (SEM) and internal particle structure (cross-section) of
sponge iron powder (NC100.24) and water-atomized iron powder (ASC100.29).
97
98
CHARACTERISTICS OF IRON AND STEEL POWDERS
Flow Rate
or rather its reciprocal value, is the time in seconds which an amount of 50 g

dry powder needs to pass the aperture of a standardized funnel. Flow rate is
influenced by type and amount of lubricant admixed to the powder. The flow
rate indicates how fast a compacting tool can be filled with powder, and thus is
a limiting factor in the compacting cycle of the powder press.
Bulk Density (Apparent Density)
is determined by filling the powder through a standardized funnel into a small

cup, leveling-off the surplus powder on top of the cup, and dividing the weight
of powder contained in the cup by the cup volume (25 cm3). Apparent density
is influenced by type and amount of lubricant admixed to the powder. The
apparent density of the powder decides about the required filling depth of the
compacting tool.
Compressibility
is the name of a curve obtained by plotting the compact densities of a series

of small cylindrical powder compacts ( 25 mm), over the applied pressures.
Compact density is the weight of a powder compact divided by its bulk volume.
Compact density is influenced by type and amount of lubricant admixed to the
powder. Green density is the compact density of a small cylindrical powder
compact ( 25 mm) pressed with a standardized pressure (typically 4.2 tons/
cm2 or 600 N/mm2).
The compressibility of the powder decides about how high a compacting
pressure is needed to achieve a desired compact density.
Green Strength
is the bending strength of a green (i.e. compacted but not sintered) rectangular
test bar. Green strength increases with increasing compact density and is
influenced by type and amount of lubricant admixed to the powder. Sufficient
green strength is required to prevent compacts from cracking during ejection
from the compacting tool and prevent them from getting damaged during
handling and transport between press and sintering furnace. The more complex
and delicate the shape of a compact, the higher its green strength should be. If
the green strength of compacts is high enough, they may even be machined prior
to sintering (e.g. undercuts, traverse slots and holes).
General Aspects
Spring Back
is the elastic expansion of a cylindrical powder compact ( 25 mm) after ejection

from the compacting die. Its value is expressed as the difference between the
Outer Diameter of the compact and the Inner Diameter of the (empty) die divided
by the ID of the die. Spring back increases with increasing compacting pressure
and is influenced by type and amount of lubricant admixed to the powder and by
the elasticity coefficient of the die material in which the powder is compacted.
The spring back value is important for calculating the exact dimensions of the
compacting tool in relation to the required dimensions of the compact.
99
100 CHARACTERISTICS OF IRON AND STEEL POWDERS
3.2 Properties of Hgans

Iron Powders
As has been mentioned in the preceding chapter, Hgans produces two different
kinds of ferrous powders:
sponge-iron powders, and
water-atomized (unalloyed and low-alloyed) iron powders.
Typical structural differences between these two kinds of powders appear on
SEM-photographs and cross-sections of representative powder particles shown
in Fig. 3.1. The external shapes of both particles are irregular and fairly similar
to one another. But the sponge iron particle has, as its name suggests, a spongy
internal structure, while the water-atomized particle is internally compact.
Both kinds of powder are specially treated to yield various standard grades
having different properties to fit different applications. These standard grades
are also used in various press-ready powder mixes, i.e. blended with lubricants
and alloying additives like graphite, copper, nickel, molybdenum, phosphorous
and others.
Properties of three sponge-iron grades NC100.24, SC100.26, MH80.23,
and of two water-atomized iron powder grades ASC100.29, ABC100.30, are
presented in the diagrams in Figs. 3.2 and 3.3 and in Table 3.1.
Properties of Hgans Iron Powders 101
Table 3.1. Properties of some Hgans Iron Powders

Powder
grade
Approx.
particle
size
range m
Apparent
density
g/cm3
Flow
s/50g
H2-loss
%
NC100.24
20 180
2.45
31
0.20
SC100.26
20 180
2.65
29
MH80.23
40 200
2.30
ASC100.29
20 180
ABC100.30
30 200
C
%
Green
density
Green
strength
1)
1)
g/cm3
N/mm2
<0.01
7.02
47
0.12
<0.01
7.12
40
34
0.32
0.08
6.292)
24 3)
2.95
24
0.08
0.002
7.20
41
3.00
24
0.06
0.001
7.28
44
compacted at 600 N/mm2 in a lubricated die.

compacted at 4.2 t/cm2 in a lubricated die.
3)
measured at a green density of 6.0 g/cm2
1)
2)
Figure 3.2. Particle size distribution, flow and apparent density of five different iron powder
grades.
Compressibility at 600 MPa
Green strength at 600 MPa
g/cm3
MPa
7,5
35
7,0
30
6,5
25
6,0
20
5,5
15
5,0
(1)
(2) (3) (4)

Powder type
(5)
10
(1)
(2)
(3)
(4)
(5)
(1)
ABC 100.30
ASC 100.29
SC 100.26
NC 100.24
MH 80.23
(2) (3) (4)

Powder type
(5)
Figure 3.3. Compressibility and green strength of five different iron powder grades.
NC100.24
is one of the most widely used grades in the manufacturing of sintered parts.
Due to the irregular surface and the spongy structure of its particles, it has high
green strength; and due to its low contents of oxygen and carbon, it has good
compressibility.
SC100.26
has the best compressibility of all Hgans sponge-iron powder grades. Its
green strength is slightly lower and its apparent density slightly higher than
for NC100.24. It is very useful in cases where parts with high density are to be
achieved in one single pressing operation.
MH80.23
is especially designed to match the requirements for self-lubricating bearings. Its

particle size range is chosen to give a pore structure optimal for this application.
MH80.23 can also be added to powder mixes in small quantities to dramatically

improve green strength.
ASC100.29
is a water-atomized iron powder which due to its high purity and its compact
particle structure has very high compressibility. ASC100.29 can be compacted
in one single pressing operation at moderate pressures to densities of up to 7.2
g/cm3.
ABC100.30
is a water-atomized iron powder of outstanding compressibility and chemical

purity. It is especially well suited for the production of high-density structural
components. Densities of up to 7.4 g/cm3 are achievable in one single pressing
operation.
1. Zn-st
2.Kenolube
3. Amide wax PM
a) sponge grade
i.e NC100.24
1. Zn-st
2.Kenolube
3. Amide wax PM
b) atomized grade
i.e ASC100.29
Figure 3.4 Influence of mixing time upon apparent density of two different iron powder
grades admixed with three different lubricants.
Apart from unalloyed iron powder grades, Hgans produces water-atomized

low-alloyed steel powders trade-name AstaloyTM and a variety of diffusion
alloyed steel powder trade-name Distaloy. (The Distaloy process has been
described in some detail in the preceding chapter).
Properties of some AstaloyTM and Distaloy powders are presented in Table 3.2.
Table 3.2. Properties of some AstaloyTM and Distaloy Powders
Powder
grade
Approx.
particle
size
range m
Apparent
density
g/cm3
Flow
s/50g
H2-loss
%
Astaloy LH
20 180
3.00
26
0.10
Astaloy Mo
20 180
3.00
25
Astaloy CrA
20 180
2.85
Distaloy SA
20 150
Distaloy DC
C
%
Green
density
Green
strength
1)
1)
g/cm3
N/mm2
<0.01
7.07 2)
20 2)
0.10
<0.01
7.10
22
27
0.13
<0.01
7.04
26
2.80
27
0.12
<0.01
7.10
40
20 180
3.05
25
0.10
<0.01
7.10
31
Distaloy AQ
20 180
3.05
27
0.10
<0.01
7.17
36
Distaloy HP
20 180
3.08
25
0.10
<0.01
7.07
29
1)
2)
compacted at 600 N/mm2 in a lubricated die.

with 0.6% Kenolube admixed
Astaloy LH
is a water-atomized steel powder alloyed with 0.90% Ni, 0.90% Mo and 0.20%
Mn. It has very good hardenability and can be used for case-hardened as well as
through-hardened parts with non-critical tolerances. Admixing Cu enables very
good sinter-hardening properties.
Astaloy Mo
is a water-atomized steel powder alloyed with 1.50% Mo. Astaloy Mo has high
compressibility, exhibits an homogeneous microstructure after sintering and has
optimal hardenability. These properties make it an excellent choice for surfacehardened components requiring high surface hardness in combination with good
core toughness.
Astaloy CrA
is a water-atomized steel powder offering very good performance for a wide

range of applications. Pre-alloyed with 1.8% Cr it offers good hardenability,
which can be further increased by adding Cu in the mix.
Distaloy SA
is based on the sponge-iron grade SC100.26, to which 1.75% Ni, 1.5% Cu and
0.5% Mo in form of very finely dispersed powders have been diffusion-bonded.
Distaloy SA is recommended for densities up to 6.9 g/cm3 after single pressing.
With additions of graphite, a tensile strength of 600 N/mm2 can be achieved
in one pressing and sintering operation and so produced parts respond well to
heat-treatment.
Distaloy DC (DC = Dimensional Control)
is based on Astaloy Mo to which 2% finely dispersed nickel powder has been

diffusion-bonded. It thus contains 2% Ni + 1.47% Mo. Parts compacted from
Distaloy DC admixed with graphite exhibit high strength and very small scattering of dimensions after sintering, independent of compact density; and the
sintered parts respond very well to subsequent heat-treatment.
Distaloy AQ
is based on the water-atomized grade ASC100.29, to which 0.5% Mo and 0.5%

Ni have been diffusion bonded. This alloy has been specifically developed for
subsequent heat-treatment, such as case hardening and through hardening.
Distaloy HP (HP = High Performance)
is based on Astaloy Mo to which 4% finely dispersed nickel powder and 2%

finely dispersed copper powder have been diffusion-bonded. It thus contains
4% Ni + 2% Cu + 1.41% Mo. Parts compacted from Distaloy HP admixed with
graphite exhibit dimensional changes close to zero during sintering and adopt
very high strength values.
More detailed information about all powder grades described above, as well as
about many other interesting powder grades and powder mixes can be obtained
from Hgans in form of special brochures and electronic data.
107
108 HGANS HANDBOK FOR SINTERED COMPONENTS
Index
cast-iron . . . . . . . . . . . . . . . . . . . . . . . . 46
CCT-diagrams . . . . . . . . . . . . . . . . 58, 66
cementite formation . . . . . . . . . . . . . . . 54
ceramic . . . . . . . . . . . . . . . . . . . . . . . . . 80
chemical composition and impurities 96
activation energy . . . . . . . . . . . . . . 30, 32

alloying methods . . . . . . . . . . . . . . . . . 85
amorphous solids . . . . . . . . . . . . . . . . . . 8
stable short-range order . . . . . . . . . . . . 8
apparent density . . . . . . . . . . . . . . . . . 98
atoms per unit cell . . . . . . . . . . . . . . . . 17
austempering . . . . . . . . . . . . . . . . . 64, 65
austenite . . . . . . . . . . . . . . . . . . . . . . . . 53
grains . . . . . . . . . . . . . . . . . . . . . . 55, 73
retained . . . . . . . . . . . . . . . . . . . . . . . 64
transformations . . . . . . . . . . . . . . . . . 53
56
51
56
56
62
56
57
bainitizing . . . . . . . . . . . . . . . . . . . . . . . 64
BCC . . . . . . . . . . . . . . . . . . . . . . . . 12, 17
BCT . . . . . . . . . . . . . . . . . . . . . . . . . 52, 54
belt furnace . . . . . . . . . . . . . . . . . . . . . 81
binary phase diagram . . . . . . . . . . . . . 37
bonding between atoms . . . . . . . . . . . . 10
covalent bond . . . . . . . . . . . . . . . . . . 11
ionic bond . . . . . . . . . . . . . . . . . . . . . 11
metallic bond . . . . . . . . . . . . . . . . . . . 11
Van der Waals force . . . . . . . . . . . . . . 10
bulk density . . . . . . . . . . . . . . . . . . 96, 98
bainite . . . . . . . . . . . . . . . . . . . . . . . . . .
bainite step . . . . . . . . . . . . . . . . . . . . .
formation . . . . . . . . . . . . . . . . . . . . . .
lower . . . . . . . . . . . . . . . . . . . . . . . . .
nose . . . . . . . . . . . . . . . . . . . . . . . . . .
upper . . . . . . . . . . . . . . . . . . . . . . . . .
bainitic steel . . . . . . . . . . . . . . . . . . . . .
carbon-steel . . . . . . . . . . . . . . . . . . . . . 46
coke breeze . . . . . . . . . . . . . . . . . . . . . . 78
compact density . . . . . . . . . . . . . . . . . . 98
compressibility . . . . . . . . . . . . . . . . . . . 98
compressibility green strength . . . . . . 96

continuous cooling transformation diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . 58
cooling curves . . . . . . . . . . . . . . . . . 38, 61
cooling rate . . . . . . . . . . . . . . . . . . . 50, 51
crack propagation . . . . . . . . . . . . . . . . 73
crude powder . . . . . . . . . . . . . . . . . . . . 80
crystal . . . . . . . . . . . . . . . . . . . . . . . . . . 12
grains . . . . . . . . . . . . . . . . . . . . . . . . . 20
lattice . . . . . . . . . . . . . . . . . . . . . . . . . 14
segregation . . . . . . . . . . . . . . . . . . . . 44
twins . . . . . . . . . . . . . . . . . . . . . . . . . 20
crystalline solids . . . . . . . . . . . . . . . . . . . 9
crystallites . . . . . . . . . . . . . . . . . . . . . . 20
Curie-point . . . . . . . . . . . . . . . . . . . . . . 46
dendrites . . . . . . . . . . . . . . . . . . . . . . . . 20
diffusion . . . . . . . . . . . . . . . . . . . . . . . . 26
coefficient . . . . . . . . . . . . . . . . . . 27, 30
equation . . . . . . . . . . . . . . . . . . . . . . . 28
Ficks first law . . . . . . . . . . . . . . . . . . 27
Ficks second law . . . . . . . . . . . . . . . 27
rate . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
self . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
surface . . . . . . . . . . . . . . . . . . . . . . . . 26
systems . . . . . . . . . . . . . . . . . . . . . . . 32
vacancy . . . . . . . . . . . . . . . . . . . . . . . 26
volume . . . . . . . . . . . . . . . . . . . . . 26, 31
dislocations . . . . . . . . . . . . . . . . . . . 21, 23
dispersion hardening . . . . . . . . . . . . . . 23
electric arc furnace . . . . . . . . . . . . . . . 83
INDEX 109
electron gas . . . . . . . . . . . . . . . . . . . . . . 11
entropy of mixing . . . . . . . . . . . . . . . . . 35
equilibrium diagram . . . . . . . . . . . . . . 46
eutectic system . . . . . . . . . . . . . . . . 38, 39
external particle shape . . . . . . . . . 96, 97
FCC . . . . . . . . . . . . . . . . . . . . . . . . 17, 19
Fe- Fe3C - diagram . . . . . . . . . . . . . . . .51
ferrite . . . . . . . . . . . . . . . . . . . 46, 49, 50
ferrite formation . . . . . . . . . . . . . . . . . 53
first and second law of thermodynamics

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
flow rate . . . . . . . . . . . . . . . . . . . . . 96, 98

free energy . . . 33, 34, 36, 37, 38, 54, 55
gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
geometrical properties . . . . . . . . . . 96, 97

grain boundaries . . . . . . . . . . . . . . 20, 31
green density . . . . . . . . . . . . . . . . . . . . 98
green strength . . . . . . . . . . . . . . . . . . . 98
growth . . . . . . . . . . . . . . . . . . . . . . . . . . 59
hardness of pearlite . . . . . . . . . . . . . . . 67
HCP . . . . . . . . . . . . . . . . . . . . . 12, 17, 19
heat treatment of steel . . . . . . . . . . . . . 63
interstitial atoms . . . . . . . . . . . . . . . . . 21
isothermal . . . . . . . . . . . . . . . . . . . . . . . 64
annealing . . . . . . . . . . . . . . . . . . . 64, 65
transformation . . . . . . . . . . . . . . . . . . 59
transformation diagrams . . . . . . . . . . 58
isothermal soft-annealing . . . . . . . . . . 64
ITT-diagrams . . . . . . . . . . . . . . . . . 58, 59
lever-rule of phases . . . . . . . . 40, 42, 44
magnetic separators . . . . . . . . . . . . . . . 80
magnetite . . . . . . . . . . . . . . . . . . . . . . . 78
martempering . . . . . . . . . . . . . . . . 64, 65
martensite . . . . . . . . . . . . . . . . . . . . 49, 53
mechanical and physical properties . . 96

metallurgical properties . . . . . . . . 96, 97
microhardness . . . . . . . . . . . . . . . . . . . 96
microstructure . . . . . . . . . . . . . . . . . . . 96
Miller indices . . . . . . . . . . . . . . . . . . . . 13
non-equilibrium diagram . . . . . . . . . . 49
non-metallic inclusions . . . . . . . . . . . . 22
octahedral . . . . . . . . . . . . . . . . . . . . . . . 53
Helmholtz free energy . . . . . . . . . . . . . 34
homogeneously alloyed powders . . . . . 85
parameters of state . . . . . . . . . . . . . . . 33
heterogeneous system . . . . . . . . . . . . . 33
hydrogen-reduced iron powder . . . . . 84
hypoeutectoid steels . . . . . . . . . . . . . . . 53
inter-metallic phase Fe3C . . . . . . . . . . 46
internal energy . . . . . . . . . . . . . . . . . . . 33
internal particle structure . . . . . . . 96, 97

interstices . . . . . . . . . . . . . . . . . . . . . . . 53
packing density . . . . . . . . . . . . . . . . . . 17
particle size distribution . . . . . . . . 96, 97

pearlite . . . . . . . . . 48, 61, 62, 67, 68,
formation . . . . . . . . . . . . . . . . . . . . . .
lamellas . . . . . . . . . . . . . . . . . . . . . . .
nose . . . . . . . . . . . . . . . . . . . . . . . . . .
phase diagrams . . . . . . . . . . . . . . . . . .
69
55
55
61
33
plastic deformation metal crystals . . . 22
polycrystalline structure . . . . . . . . . . . 20
110 HGANS HANDBOK FOR SINTERED COMPONENTS
powder mixes . . . . . . . . . . . . . . . . . . . . 86
quenching and tempering . . . . . . . . . . 64
reduction mix . . . . . . . . . . . . . . . . . . . . 80
ring-shaped nozzle . . . . . . . . . . . . . . . . 83
tie-line . . . . . . . . . . . . . . . . . . . . . . . . . . 39
transformation diagrams . . . . . . . . . . 58
transition points A3 and A1 . . . . . . . . . 50
trostite . . . . . . . . . . . . . . . . . . . . . . . . . . 50
TTT-diagrams . . . . . . . . . . . . . . . . 49, 58
twinning . . . . . . . . . . . . . . . . . . . . . . . . 20
rotary dryers . . . . . . . . . . . . . . . . . . . . 80
unit cell . . . . . . . . . . . . 13, 15, 17, 18, 53
self-tempered martensite . . . . . . . . . . . 57
slip plane . . . . . . . . . . . . . . . . . . . . . . . 22
solidus . . . . . . . . . . . . . . . . . . . . . . . . . . 36
sorbite . . . . . . . . . . . . . . . . . . . . . . . . . . 50
space lattice . . . . . . . . . . . . . . . . . . . . . 13
spheroidite . . . . . . . . . . . . . . . . . . . . . . 67
spheroidized cementite . . . . . . . . . . . . 67
sponge-iron powders . . . . . . . . . . . . . 100
sponge-iron process . . . . . . . . . . . . . . . 78
spring back . . . . . . . . . . . . . . . . . . . . . . 99
stable system . . . . . . . . . . . . . . . . . 46, 47
stacking sequence . . . . . . . . . . . . . . . . .18
starmix . . . . . . . . . . . . . . . . . . . . . . . . 93
stationary case . . . . . . . . . . . . . . . . . . . 27
substitutional atoms . . . . . . . . . . . 21, 26
supersaturation . . . . . . . . . . . . . . . . . . 54
surfaces . . . . . . . . . . . . . . . . . . . . . . . . . 31
temper brittleness . . . . . . . . . . . . . . . . 73
tempered martensite . 56, 57, 70, 72, 73

tetragonal distortion . . . . . . . . . . . . . . 52
tetragonally distorted ferrite . . . . . . . 56
tetragonal martensite lattice . . . . . . . . 52
tetrahedral . . . . . . . . . . . . . . . . . . . . . . 53
thermal analysis . . . . . . . . . . . . . . . . . . 38
thermodynamic . . . . . . . . . . . . . . . . . . 33
equilibrium . . . . . . . . . . . . . . . . . . . . 33
state . . . . . . . . . . . . . . . . . . . . . . . . . . 33
undercooling . . . . . . . . . . . . . . . . . . 50, 51
vacancies . . . . . . . . . . . . . . . . . . . . . . . . 21
water-atomized . . . . . . . . . . . . . . . . . 100
water-atomized process . . . . . . . . . . . . 82
yield point . . . . . . . . . . . . . . . . . . . . . . . 25
INDEX 111
112 NOTES
Power of Powder
Metal powder technology has the power to open up a world
of possibilities. The inherent properties of metal powders provide
unique possibilities to tailor solutions to match your requirements.
This is what we call Power of Powder, a concept to constantly
widen and grow the range of metal powder applications.

With its leading position in metal powder technology, Hgans
is perfectly placed to help you explore those possibilities as your

application project partner.

Power of Powder is being applied far beyond its traditional
role in the production of components for vehicles. Iron powder

is used in food fortification to combat anaemia. Nickel powders
are vital ingredients in valve coatings to enhance wear resistance.
Specially formulated iron-based powders offer new solutions for
high-temperature brazing. Soft Magnetic Composites with 3D
magnetic properties are opening the way for innovative electric
motors. In fact, metal powder technology generates virtually
endless possibilities.

To find out how you can apply the Power of Powder, please
contact your nearest Hgans office.
www.hoganas.com/pmc

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Power of Powder

Metal powder technology has the p

Hgans Handbook for Sintered Components

Material and Powder Properties

Production of Sintered Components

Compacting of Metal Powder

Design and Mechanical Properties

Material and powder properties

Production of Iron and Steel Powders . . . . . . . . . 75

Characteristics of Iron and Steel Powders . . . . . . . 95

This chapter presents a selection

The Natural States of Matter . . . . . . . . . . . . . . 8

1.1 The Natural States of Matter

The Natural States of Matter

1.2 The Crystalline Structure

1.2.1 Bonding Between Atoms

Crystal structures owe their existence to various types of interatomic forces

The Crystalline Structure of Metals

* W. Schatt: Einfhrung in die Werkstoffwissenschaft. VEB Deutscher Verlag fr Grundstoffindustrie,

The Crystalline Structure of Metals

1.2.2 Ideal Crystals

A crystal structure has three general properties: periodicity, directionality and

Figure 1.3. Lattice planes (LP)

The Crystalline Structure of Metals

Figure 1.4. Derivation

Figure 1.6. Lattice points and lattice

For the characterization of lattice planes, directions and points in hexagonal

The Crystalline Structure of Metals

In the case of the BCC-cell, putting together an eighth of an atom from

The Crystalline Structure of Metals

The stacking sequence ABABAB forms the HCP-structure, and ACBACBACB

1.2.3 Real Metal Crystals

The Crystalline Structure of Metals

(2-2) interstitial atom,

Zero-dimensional lattice disturbances are

One-dimensional lattice disturbances are so-called dislocations which occur

Two-dimensional lattice disturbances are the above mentioned grain boundaries,

Figure 1.12. Two-dimensional lattice

Three-dimensional lattice disturbances are non-metallic inclusions, dislocation

1.2.4 Plastic Deformation of Metal Crystals

The Crystalline Structure of Metals

Figure 1.13. Atomic bonds

Along a dislocation line perpendicular to the direction of slip, bonds are

In order to achieve a noticeable plastic deformation, a great many dislocation

When the temperature is raised, dislocations gradually dissemble as atoms escape

The Crystalline Structure of Metals

See Fig. 1.16. Dissembling of jammed and entangled dislocations is the

Figure 1.16. Dislocation climbing:

1.3 Diffusion in Metals

1.3.1 Laws of Diffusion

In heterogeneous materials, concentration differences tend to level, because an

1.3.2 A Particular Solution of the Diffusion Equation

Remarkable with equation (1.4) is the circumstance that the concentration

1.3.3 The Diffusion Coefficient

The diffusion coefficient D is a measure of the diffusion rate. D depends on

Diffusion coefficients D, material constants D0 and activation energies Q for

Binary Phase Diagrams of Metals

1.4 Binary Phase Diagrams

First of all, some definitions are required:

d G = d(E - ST + PV) = d F + d(PV) (1.8)

dG = d(E ST + PV) 0 (1.9)

Binary Phase Diagrams of Metals

1.4.2 Derivation of Binary Phase Diagrams

Applying the thermodynamic rules discussed in the preceding paragraph to a