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Introduction To Metallurgy
Introduction To Metallurgy
INDEX
Page
1.
Introduction.................................................................................................4
1.1
1.2
1.3
1.4
2.
Equilibrium Diagrams...............................................................................10
2.1
2.2
2.3
2.4
3.
Stress Relief..............................................................................17
Recrystallisation........................................................................17
Grain Growth.............................................................................18
5.
4.
Metals .........................................................................................4
Alloys ..........................................................................................7
Solid Solutions............................................................................7
Phase Mixtures............................................................................8
Heat Treatment..........................................................................................24
5.1
Hardening Mechanisms.............................................................24
5.1.1
5.1.2
5.1.3
5.1.4
5.2
Isothermal Transformations.......................................................29
5.2.1
5.2.2
5.2.3
5.3
5.4
5.5
5.6
5.7
6.
Normalising...............................................................................31
Full Annealing...........................................................................31
Quenching and Tempering........................................................34
Importance of Grain Size...........................................................35
Grain Size Determination..........................................................37
Alloying......................................................................................................39
6.1
6.2
6.3
Carbide Formers......................................................40
Crystal Growth.........................................................41
Corrosion Resistance..............................................42
Strength...................................................................42
7.
TTT Curves..............................................................29
Continuous Cooling Transformation Curves............30
Effects of Alloys on Transformations........................30
Carbon.....................................................................42
Manganese..............................................................42
Chromium................................................................43
Nickel.......................................................................43
Molybdenum............................................................44
Niobium...................................................................44
Vanadium.................................................................45
Aluminium................................................................45
Sulphur....................................................................45
Phosphorus.............................................................46
Silicon......................................................................47
Weld Metal................................................................................49
Heat Affected Zone....................................................................51
Welding Heating Cycle..............................................................52
Carbon Equivalent.....................................................................53
8.
Structure of Ingots....................................................................................54
8.1
8.2
8.3
Pipe...........................................................................................54
Segregation...............................................................................55
Steel Types...............................................................................56
8.3.1
8.3.2
8.3.3
Rimming Steel.........................................................56
Semi-killed Steel......................................................57
Killed Steel...............................................................57
1.
INTRODUCTION
1.1
Metals
Metals are chemical elements or alloys, which in general exhibit the following
properties:
-
High densities
Reflect light and are generally white in colour -except Gold and Copper
Magnetic to some degree but only Iron, Nickel and Cobalt are ferro
magnetic
Face-centred cubic
- Iron (austenite)
Copper
Silver
Gold
Aluminium
Lead
Nickel
Platinum
The most economical packing arrangements for the metal atoms are the
hexagonal close packed and face centred cubic, followed the body centred
cubic structure, which occupies a larger volume (Fig 1).
Fig 2
Fig 3
The importance of different packing densities is illustrated by the fact that the
metal iron is allotropic, that is it adopts different crystal structures according to
its temperature. Up to a temperature of 910C it has a body-centred cubic
form, from 910C to 1400C it is face centred cubic, and above 1400C it
reverts to body centred cubic until it melts at about 1535C. Heating the
metal will not only produce an increase in volume by thermal expansion, but
also, volume changes will be caused by alterations in crystal structure.
The diagram (Fig 2) demonstrates the volume effects of different atomic
packing arrangements resulting from the allotropic changes from body
centred cubic structure to face centred cubic structure and back to body
centred cubic structure.
When a metal alloy solidifies, each crystal begins to form independently from
a nucleus or centre of crystallisation. The nucleus will be a simple unit of
appropriate crystal lattice, and from this the crystal will grow. It develops by
the addition of atoms according to the lattice pattern and rapidly begins to
assume visible proportions in what is called a dendrite. (Dendritic-tree-like).
A metallic crystal grows in this way because heat is dissipated more quickly
from a point, leading to the formation of a rather elongated skeleton (Fig 3).
The dendrite arms continue to grow and meet neighbouring dendrites which
will be orientated differently owing to their independent formation; that is, their
lattices will meet at odd angles. Hence the independent formation of each
crystal leads to the irregular overall shape of crystals and to the characteristic
grain structure of metals when in the as cast condition.
1.2
Alloys
An alloy is essentially a mixture of two or more elements, the principal
component being a metallic element (the 'parent metal' or 'solvent'), so that
the resultant mixture exhibits metallic properties. A wide variety of mechanical
and physical properties may be obtained by alloying, so that alloys, rather
than pure metals, are of the greatest importance for engineering.
If the constituent metallic atoms are chemically similar to one another, they
will crystallise as a single set of crystals, since all the atoms will behave as if
they belonged to the same species. A single-phase solid solution is then
said to form, and its microstructure is often indistinguishable from that of a
pure metal.
However, there may be a tendency for the elements to crystallise separately
to form distinct and different crystals joined at mutual grain boundaries. Such
a structure is an example of a phase mixture, which can usually be
distinguished from a single-phase solid by metallographic examination.
Note that this could include the formation of an intermetallic compound.
These compounds are in themselves of little practical value, since they tend
to be hard and brittle, but they can be important as constituents of alloy
systems.
1.3
Solid Solutions
Initially when a solid solution is formed the crystal structure is the same as
that of the parent metal - the atoms of the solute or alloying element are
distributed throughout each crystal, and a range of composition is possible.
The solution may be formed in two ways:
(a)
(b)
(a)
substitutional
(b)
interstitial
Phase Mixtures
A phase, present in an alloy as a separate entity, can be pure metal, a solid
solution or an intermetallic compound. Any mixtures of two or more of these
can occur. In binary systems, that is those of two elements, generally not
more than two phases can exist together.
2.
EQUILIBRIUM DIAGRAMS
Thermal equilibrium (also known as Phase or Constitutional) diagrams are
of great importance in metallurgy for with their aid it is possible to determine
exactly the structure of a particular alloy at any given temperature, provided
the alloy has been allowed to reach a state of equilibrium. Thus the phases
present, their quantities and the chemical composition of each phase can be
shown with precision. The diagrams are constructed principally by thermal
analysis but also with microscopic studies, the examination of volume
changes, X-ray diffraction and other techniques.
Equilibrium can be considered as a state of balance ultimately arrived at by
the components at the temperature of the system concerned. However, in
some cases such a state would take a very long time to be reached while in
others it may never be reached at the temperature in question. For example,
if an alloy is rapidly cooled by quenching to room temperature, chemical and
physical changes may be suppressed such that they will never take place
unless the alloy is reheated to allow them to occur. Very slow cooling must
then follow.
2.1
Fig 5
10
Fig 6
Note that the Lower Critical Temperature 723C below which all Austenite has
been converted to Ferrite and Cementite is commonly known as the A1
temperature. The temperature above which the structure will be wholly
Austenite, the Upper Critical Temperature, is known as the A3 temperature.
Also the temperature above which the steel reverts to a wholly body centred
cubic ferrite is known as the A4 temperature.
2.2
Continued cooling and precipitation of ferrite will increase the carbon content
of the austenite until it reaches that of the eutectoid 0.83%C. At 723C this
remaining austenite will transform to pearlite resulting in a final structure of
ferrite plus pearlite.
2.3
Quenched Structures
The previous microstructures form in plain carbon steels which have been
moderately slowly cooled (e.g. by cooling in air) from temperatures within the
austenitic phase field, say from 50C above the lower boundary line CED.
This is called a 'normalising' heat treatment, but medium and high-carbon
steels are very commonly subjected to more complex treatments in order fully
to exploit their properties. These treatments involve, first, heating the alloy
into the austenite phase field, as before, but then quenching it in water or
brine which suppresses diffusion and thus the formation of ferrite and
cementite. Under these conditions the austenite transforms by a process not
involving diffusion into a metastable distorted form of body-centred iron
known as 'Martensite' (Fig 7d). This process is extremely rapid and the
transformation may be completed in a few microseconds.
Fig 7a
Fig 7b
12
Fig 7c
Fig 7d
Martensite (2000X)
13
2.4
Critical Temperatures
There has been reference to the A1 lower critical temperature, the A3 upper
critical temperature and the A4 temperature above which austenite reverts to
ferrite. Examination of the Iron-Carbon equilibrium diagram shows that the
latter change will not occur when the carbon content approaches and
exceeds 0.5%C. In such cases liquid steel will solidify directly to austenite.
Concern may be felt regarding the non-appearance of an A2 temperature and
also the absence of a beta phase in the equilibrium diagram. Originally the
designation A2 was given to the temperature 769C, the Curie point, at which
iron ceases to be magnetic, a fact that was expected to be accompanied by a
phase change. This proved not to be the case and the A2 has no structural
significance.
It cannot be emphasised too strongly that the structural changes in the
diagram and the temperatures at which they occur refer to conditions of
equilibrium. In practice it is found that, on heating, it is necessary to exceed
the equilibrium temperatures to achieve the expected structural changes.
Such temperatures would normally be about 50C above the A1 and A3 and
can be determined with reasonable accuracy for particular conditions of
heating. Here the lower critical point is termed the Ac1 and the upper critical
point the Ac3 temperature. The suffix C has been derived from the French
chauffage meaning heating. In a similar way it may be expected that on
cooling it is necessary to reach temperatures lower than those of the
equilibrium diagram to obtain the appropriate structural changes. Thus, for
example, in hot rolling operations, which are accompanied by continuous
cooling, temperatures of 100-150C below equilibrium become necessary for
the expected structural changes. In such cases AR1 and AR3 temperatures are
referred to, the suffix R again being French, derived from Refroidissement,
cooling.
The Effect of Heating Rates on Lower and Upper Critical Temperatures
Steel AISI 1045 (0.45%C)
Equilibrium Temperature
30
300
1400
Ac1
723
780
790
800
840
Ac3
770
820
830
860
935
14
3.
3.1
3.2
Stage II - Recrystallisation
As mentioned previously, a low-temperature anneal to relieve internal stress
may sometimes be used, but generally annealing involves a definite and
observable alteration in the crystal structure of the metal. If the annealing
temperature is increased a point is reached when new crystals begin to grow
from nuclei produced in the deformed metal. These nuclei are formed at
points of high energy, such as crystal boundaries. The crystals so formed are
at first small, but grow gradually until they absorb the entire distorted structure
produced originally by cold-work. The new crystals are equi-axed in form,
that is, they do not show any directional elongation, as did the distorted coldworked crystals which they replace.
This phenomenon is known as recrystallisation, and it is a method
employed, in conjunction with cold-work, of course, to produce a fine-grained
structure in non-ferrous metals and alloys. Only in some cases - notably in
15
steels and aluminium bronze, where certain structural changes take place in
the solid state - is it possible to refine the grain size by heat-treatment alone.
3.3
16
4.
17
4.1
4.2
170
293
388
HARDNESS
ROCKWELL
C
5
31
41
Feathery
bainite (upper)
Acicular
bainite (lower)
Bainite
&
Martensite
Martensite
401
415
555
578
601
42
44
56
58
60
500
400
280
230
175
682
66
RT
18
TEMPERATURE OF
TRANSFORMATION
C
720
660
580
4.3
Hardenability
Hardenability is a measure of the depth a steel will harden on quenching.
The uniform rapid cooling of a heavy steel section is impossible even with
drastic quenching. Such a section will not harden completely to its core
whereas a thin section would be wholly martensitic. This difficulty can
however be overcome by the addition to the steel of alloying elements which
will in general increase the time available to begin and complete
transformation. Thus a martensitic structure becomes possible with the lower
cooling rates found in heavier sections. This is one of the most important
functions of alloying and to ensure the correct application of such steels, from
both the technical and economic aspects, some measure of hardenability
becomes necessary. To determine this, tests have been devised to estimate
the maximum diameter at which the required structures can be produced by
quenching. If this diameter is exceeded, hardening at the core will be
incomplete resulting in non-uniform properties.
The Jominy end-quench test (Fig 9) is widely used in evaluating the
hardenability of steel. Here a standard test piece is heated to its austenitic
region, dropped into a frame and quenched, at one end only, by a measured
jet of water at 25C. Thus different rates of cooling are obtained along the
length of the bar and the resulting hardness values can be determined. The
drawings illustrate the test and the graphs show typical hardness values from
the tests of three steels of differing compositions (Fig 10). It will be noted that
the depth of hardening increases markedly with growing alloy content even
though the proportion of carbon at 0.45% is the same in each case. Using
the Jominy test results as a basis it is possible, for a particular steel, to
calculate a maximum diameter at which uniform properties can be obtained.
Such a measure is known as the ideal diameter or ruling section. The ideal
diameter here represents the section at which a structure of 50% martensite
is achieved.
19
(A)
(B)
Fig 9
20
21
5.
HEAT TREATMENT
5.1
Hardening Mechanisms
It has been calculated that the theoretical strengths of pure metals should be
much greater than those observed.
These differences have been
convincingly explained by dislocation theory.
This theory has been likened to a situation where one carpet lying on top of
another is very difficult to move by pulling at one end. However a ruck in the
upper carpet will move across it very easily. This ruck represents the
dislocation moving between slip planes in a metal giving rise to plastic
deformation, which otherwise could not occur. Calculations confirm that the
stress required to make the dislocation lines move is in good agreement with
the measured yield stress so that such faults can account for the weakness of
metals. The dislocation lines finish only when they reach a metal surface or
grain boundary. If dislocation motion is impeded, for example by interaction
with other dislocations, there will usually be an increase in hardness and
strength. It should be emphasised that dislocation theory is much more
complex than this grossly over-simplified version (Fig 11).
Fig 11
5.1.1
very steep rise in yield strength with increasing solute. If only a very small
quantity of such a solute is present one effect of this high local strain is that
the solute element will tend to migrate to the space provided along the
dislocations present rather than being uniformly distributed in solution in each
crystal. This has the effect of pinning (holding) the dislocations in place, a
phenomenon which is revealed by the presence of a Yield Point when plastic
flow sets in during a tensile test.
Substitutional solute addition is the commonest way of solution-hardening a
metal. Brass (copper-zinc) and bronze (copper-tin) are two familiar materials
which make use of this hardening effect.
5.1.2
Precipitation Hardening
Thermal treatment can be used to control the size and distribution of second
phase particles in any alloy which undergoes a phase transformation in the
solid state. Alloy systems which have a phase diagram showing a decreasing
solid solubility limit with decreasing temperature are particularly appropriate
for such treatments and particles of the second phase can often be made to
precipitate in a very finely dispersed form.
In Figure 12, an alloy C exists as a single phase solid solution () at high
temperatures but on slow cooling it becomes supersaturated with respect to
the second phase, which therefore separates out.
The distribution of the phase may be controlled as follows.
The alloy is first solution heat-treated at the high temperature and then rapidly
cooled by quenching into water or other cooling fluid. Solid-state diffusion is
suppressed in this way, so that the phase cannot separate and the alloy
exists at the low temperature in an unstable supersaturated state. If the
temperature is now increased, so that diffusion can take place at a
measurable rate, the second phase will nucleate and grow.
In alloys of relatively low melting-point, there will be an appreciable diffusion
rate of solute atoms at room temperature, so that over a sufficient length of
time, the second phase will precipitate out. This effect is known as 'ageing',
but in most alloys the temperature has to be raised in order to cause
precipitation to occur and the material is said to be 'artificially aged'. The
rate of growth of the precipitate is controlled by the rate of atomic diffusion, so
that the precipitation increases with increasing ageing temperature. The size
of the precipitate becomes coarser as the ageing temperature is increased,
as shown schematically in Fig 12.
If, at any temperature, the time of heat treatment is very prolonged,
coagulation or coarsening of the particles occurs; the small ones tend to
redissolve and the large ones to grow at their expense.
Precipitation hardening is the term now used to describe ageing. Just as
heating will accelerate precipitation hardening, refrigeration will impede the
process.
23
Fig 12
24
5.1.3
Work Hardening
Owing to the interaction of dislocations within the grains, plastic deformation
will progressively harden a metal. The dislocations will multiply with strain
and their density will continually rise with increasing deformation and thus the
number of interactions per unit volume will rise as the strain continues. When
a polycrystalline metal is stressed, each grain is deformed into a shape that is
dictated by the deformation of its neighbours which requires the operation of
several slip systems. The following graphs given in Figs 13, 14 and 15 show
the effects of cold work on mechanical properties.
Ultimate tensile strength can be increased by up to 1040 N/mm2 by reducing
the cross-section by cold working by 90%. A reduction in cross-section by
10% will reduce percentage elongation from about 30% to 4%. Thereafter
there will be little decrease to about 2%.
25
Fig 14 Effect of cold deformation on the strength and hardness of metal. It will
be seen that the spread between the yield strength and tensile strength curves
becomes less with greater amounts of deformation and a consequent
reduction in ductility.
26
5.1.4
0.20%C
140
280
450
0.80%C
200
350
700
Strain Ageing
Strain ageing is observed when low carbon steel has been subjected to a
small amount of deformation and then allowed to age for a period. This
results in an increase in hardness and strength with reduced ductility and a
drastic reduction of toughness as measured by impact tests. Even less than
1% cold reduction can produce such ageing which can be attributed largely to
the movement of nitrogen atoms in the steel to sites which allow dislocations
to be pinned in place. The maximum effect is with about 15% reduction.
Such ageing proceeds very slowly at room temperatures and may take
several months to reach a peak. Temperature increases will however rapidly
increase the rate of hardening and at 300C this will reach the maximum
value in a few seconds.
5.2
Isothermal Transformations
So far consideration has been given to very slow cooling, when conditions will
approach equilibrium, or very fast cooling to ambient temperatures. Variations
in cooling rates between these extremes are possible and the results can be
shown in isothermal transformation curves, also known as S curves, or timetemperature-transformation (TTT) curves. These are constructed by taking a
number of specimens of the steel in question, heating them into the austenitic
range and then quenching them in baths of different temperatures. At
predetermined time intervals individual specimens are taken from their baths
and quenched in water. They are then examined microscopically to evaluate
the extent of the transformation that has occurred.
5.2.1
27
it occurs almost instantly. The degree to which this change takes place is
determined simply by the temperature to which the steel is cooled. Once a
transformation has gone to completion a steel will usually be water quenched
with no further change in its constitution.
28
5.2.3
5.3
Normalising
The process refers only to steel and consists of heating the metal to a
temperature about 50C above its Upper Critical Point (Ac3 temperature) or
austenitising temperature and having given adequate time for full conversion
to Austenite allowing it to cool in still air. On heating, the change from body
centred to face centred cubic structure will result in small austenite crystals
whose sizes will determine those of the body centred cubic crystals formed on
cooling. The process is therefore important in producing a refined grain size.
If too high a temperature is employed, grain growth of the austenite will occur
which will be reflected in the final cooled structure.
5.4
Full Annealing
This process is also applicable only to steel and consists of heating the
material to the appropriate normalising temperature and then cooling it very
slowly (Fig 18), usually in the furnace. The resulting structure, as with
normalised steel, will consist of ferrite or cementite with grains of pearlite but
full annealed steel will be expected to have a somewhat larger grain size.
More important is the effect of slow cooling on the structure of pearlite and
this will become more coarsely lamellar with decreasing cooling rate which
may even lead to very coarse lamellae balling up into coalesced particles of
cementite in a groundmass of ferrite. Steel subjected to full annealing
treatment will have lower tensile strength, impact strength and yield point but
higher elongation values than those of normalised steel.
29
30
Fig 18
(A)
(B)
(C)
(D)
Normalised
Fully Annealed
Water-quenched
Water-quenched and tempered
31
5.5
5.6
0.40%C Steel
As Quenched
200C
350C
450C
600C
Hardness HV
Tensile N/mm2
Elongation %
Charpy Impact (J)
670
1850
5
11
620
1700
12
19
440
1420
14
14
370
1200
16
30
220
880
24
75
Fig 20 Schematic representation of the effect of temperature and grainrefining elements on grain size
33
34
Of the three methods listed in the standard, the comparison procedure is most
popular since it takes the least time to carry out. This method involves viewing
grains in a microscope and comparing them at the same magnification, 75X or
100X, to charts defined in ASTM E112, with two examples shown in Figure 21.
The ASTM Grain Size Number corresponds to a certain number of grains/in 2
according to Table below:
0
0.5
1
1
2
2
3
4
4
8
5
16
6
32
7
64
8
128
9
256
10
512
The relationship between the Grain Size Number and the number of grains/in 2
is given by the expression:
Where:
N = ASTM Grain Size Number n = 2 (N 1)
n = number of grains/in2 at the specified magnification
35
6.
ALLOYING
6.1
36
6.1.1
37
Crystal Growth
The rate of crystal growth is accelerated, particularly at high temperatures, by
the presence of some alloy additions, notably chromium. Care must therefore
be taken that steels containing elements in this category are not overheated
or, indeed, kept for too long at an elevated temperature, or brittleness, which
is usually associated with a coarse grain size, will result.
Fortunately, grain growth is retarded by other elements, notably niobium and
vanadium, whose presence thus produce a steel which is less sensitive to the
temperature conditions of heat-treatment.
38
6.1.3
Corrosion Resistance
The corrosion-resistance of steels is substantially improved by the addition of
aluminium, silicon and chromium. These metals form thin but dense and
adherent oxide films which protect the surface of the steel from further attack.
Of the elements mentioned chromium is the most useful when mechanical
properties have to be considered. When nickel also is added in sufficient
quantities, the austenitic structure is maintained at room temperature.
6.1.4
Strength
One of the main reasons for alloying is to effect improvements in the
mechanical properties of steel. These improvements are generally the result
of physical changes already referred to. For example, hardness is increased
by stabilising the carbides; strength is increased when alloying elements
dissolve in the ferrite; and toughness is improved by refinement of the grain
size.
6.2
6.2.1
Carbon
It has been shown that increasing carbon content in plain carbon steels will
lead to increases in hardness and, up to the eutectoid composition (0.83%C)
increases the tensile and yield strengths. Corresponding to these changes
will be decreases in ductility, malleability and impact strength. Increasing the
carbon content of martensitic steels may be expected to show increases in
hardness up to the eutectoid point. Tempered martensitic structures will show
increases in hardness and brittleness up to about 1.4%C. Hardenability in
plain carbon steels is at a maximum at the eutectoid composition. Increasing
or decreasing the carbon content from the eutectoid composition will lead to
lower hardenability, i.e. it becomes increasingly more difficult to obtain
martensitic structures, and increasingly rapid quenching is required.
6.2.2
Manganese
Some manganese is present in nearly all steels. It is usually below 1% and it
is only when this amount is exceeded that it is regarded as a deliberately
added alloying element. Like nickel, manganese stabilises austenite but
unlike nickel it also has the effect of stabilising the carbides, by itself forming
Mn3C. It has a considerable strengthening effect on ferrite and increases
hardenability.
39
6.2.3
Chromium
Very small amounts of chromium when added to carbon steel will cause a
considerable increase in hardness. At the same time strength is raised with
some loss of ductility which is not apparent with less than 1.0%Cr. The
increase in hardness is mainly due to the fact that chromium is a carbide
stabiliser forming hard carbides itself or double carbides with Fe 3C.
Chromium is a ferrite stabiliser and austenite may be eliminated entirely when
more than 11%Cr is added to pure iron.
The main disadvantages in the use of chromium as an alloying element is its
tendency to promote grain growth, with its attendant brittleness. Care must
therefore be taken to avoid overheating or holding for too long at the normal
heat-treatment temperature.
Steels containing small amounts of chromium and up to 0.45% carbon are
used for axle shafts, connecting-rods and gears; whilst those containing more
than 1.0% carbon are extremely hard and are useful for the manufacture of
ball-bearings, drawing dies and parts for grinding machines.
Chromium is also added in larger amounts - up to 21% - and has a
pronounced effect in improving corrosion-resistance, due to the protective
layer of oxide formed. This oxide layer is extremely thin, and these steels
take a very high polish. They contain little or no carbon and are therefore
completely ferritic and non-hardening (except by cold-work).
Stainless steels which have only chromium as the main alloying element and
have C levels that exceed 0.1% are of the martensitic type, the structure
being obtained by rapid cooling. If these steels are allowed to cool slowly,
carbides will be precipitated, with consequent loss in corrosion-resistance
(sensitisation).
6.2.4
Nickel
The addition of nickel to a plain carbon steel tends to stabilise the austenite
phase.
For example, the addition of 25% nickel to pure iron renders it austenitic, and
so non-magnetic, even after slow cooling to room temperature.
Nickel makes the carbides unstable and tends to cause them to decompose
to graphite. It is therefore inadvisable to add nickel by itself to high carbon
steels and most nickel steels are of the low carbon type. Generally the 3.5%
nickel steels are the most widely employed, those with about 0.12%C being
used mainly for case hardening, while the 0.30%C types are used for
structural purposes and in engines for shafting and axles etc. Nickel also has
a grain refining effect enabling the alloys to be employed in case hardening
as grain growth will be limited during prolonged treatment at about 900C.
40
Nickel was one of the first elements added to plain carbon steels, its main
advantage being to increase tensile strengths without adversely affecting
ductility. Its effect of lowering critical temperatures for heat treatment is also
an advantage in cost reduction.
Nickel in moderate amounts also increases hardenability allowing slower
quench rates than in plain carbon steels.
6.2.5
Molybdenum
Molybdenum is a strong carbide stabiliser and relatively small amounts will
markedly enhance the properties of plain carbon steels. Usually it is added in
quantities ranging from 0.12-0.65% depending on the intended application of
the steel. More often it is used in combination with manganese, nickel and/or
chromium to give a noticeable improvement in properties. Hardenability is
increased especially when used in conjunction with chromium. One of the
metal's advantages is that it will reduce the tendency to temper brittleness in
low nickel low chromium steels when heat treated at 250-400C. In general
Ni-Cr-Mo alloy steels possess the best all-round combination of properties,
especially when high tensile strength and good ductility are required in large
components. Such steels are relatively free from the mass effects of heat
treatment, the transformation rates of the Ni-Cr steels being even further
reduced by the presence of molybdenum which contributes considerably to
hardenability. Its presence will also raise the high temperature strength and
creep resistance of high temperature alloys and it is added to stainless steels
in proportions of up to 3.0% to improve corrosion resistance especially in
chlorides and acids.
The disadvantages of molybdenum steels are that they require higher
tempering temperatures to obtain properties comparable to plain carbon
steels and they need a longer holding period at quenching and normalising
temperature to ensure complete solid solution of the molybdenum iron
carbide.
6.2.6
41
6.2.7
Vanadium
Plain vanadium steels are manufactured to a very limited extent, but
chromium-vanadium steels containing up to 0.2% vanadium are widely used
for small and medium sections. The mechanical properties resemble those of
nickel-chromium steels, but usually show an advantage in respect of the limit
of proportionality and percentage reduction in area. Chromium-vanadium
steels are also easier to forge, stamp and machine, but are more susceptible
to mass effects of heat-treatment than the corresponding nickel-chromium
steels.
Vanadium has a strong carbide-forming tendency. It also stabilises martensite
and low temperature tempered martensite on heat-treatment and increases
hardenability. Like nickel, it restrains grain growth of the austenite. One of
the most important effects of vanadium is that it induces resistance to
softening at high temperatures provided that the steel is first heat-treated to
absorb some of the vanadium carbide into solid solution. Consequently
vanadium steels are used for hot-forging dies, extrusion dies, die-casting dies
and other tools operating at elevated temperatures.
6.2.8
Aluminium
The presence of aluminium in plain carbon and low alloy steels will tend to
stabilise ferrite but as it will normally be in very low concentrations (<0.050%)
its direct effect on hardenability will be negligible. It can however act as a
strong grain refiner (levels >0.015%) which may reduce hardenability
somewhat although improving tensile and impact strengths. It is widely used
as a deoxidant in low carbon mild steels where ductility is the principal quality.
In such steels the presence of small amounts of nitrogen introduced during
steel making will cause strain ageing to the detriment of their properties. A
small amount, up to about 0.08%, of residual aluminium by forming aluminium
nitride will suppress this phenomenon in cold rolled annealed tempered
grades. In offshore structures a Al to N ratio of at least 2:1 is sometimes
specified to overcome strain ageing during welding.
6.2.9
Sulphur
The element sulphur will tend to decrease hardenability somewhat, but as,
with a few exceptions, considerable efforts are made to eliminate it from plain
carbon and alloy steels, it is usually present only in small amounts and its
effect in this respect may be neglected.
It is the most deleterious impurity commonly present in steel. If precautions
are not taken to render it harmless it will form the brittle sulphide, FeS. This is
soluble in molten steel, but when solidification takes place the solid solubility
falls to an equivalent of 0.03% sulphur. If the effects of extensive coring are
also taken into account amounts as low as 0.01% sulphur may cause
precipitation of the sulphide at the grain boundaries. In this way the austenite
grains will become virtually coated with brittle films of ferrous sulphide. Since
this sulphide has a fairly low melting point, the steel will tend to crumble
during hot-working. Being brittle at ordinary temperatures, ferrous sulphide
42
will also render steel unsuitable for cold-working processes, or, indeed, for
subsequent service of any type.
The sulphur is rendered harmless by the presence of manganese with which it
combines preferentially to form manganese sulphide MnS. This MnS is
insoluble in molten steel and some will be lost in the slag while the rest will be
present as globules distributed throughout the steel and not associated with
the structure when solidification takes place. These globules are plastic at hot
working temperatures and the tendency of the steel to crumble is thus
removed while the globules will be rolled out as threads in subsequent
operations.
With modern steel making practices levels of <0.01%S and 0.02%P are
commonly achieved. The demand for high grade weldable steels for stringent
applications such as off-shore pipelines has led to the availability of grades
with less than 0.01%S and 0.01%P. These have become possible largely by
the selection of high-grade raw materials which themselves have low
proportions of these elements and the introduction of new steelmaking
techniques the most notable being vacuum degassing. With such steels MnS
will also be low which will reduce the extent of non-metallic inclusions with
consequent benefits to weldable steels for critical structural applications.
Free cutting steels are made with a deliberately high level of sulphur, from
0.15-0.25%S in plain carbon steels, with about five times the manganese
content to ensure its presence a globular MnS. This sulphide is widely
distributed so that on machining the cutting tool forms small chips which are
easily handled.
6.2.10
Phosphorus
In the same way as sulphur, phosphorus is almost always considered an
undesirable element in steel and its proportion is usually kept to a minimum.
It will increase hardenability but as it is present in such a small amount its
effect and that of sulphur are generally thought to cancel each other out.
Phosphorus forms the brittle phosphide Fe3P, which is soluble in ferrite. In
solution, it has a considerable hardening effect but it must be rigidly controlled
to amounts in the region of 0.05% or less because of the brittleness also
introduced, particularly if Fe3P should appear as a separate constituent in the
microstructure. Nowadays 0.02% is commonly produced and high grade
materials with 0.01%P are available.
43
6.2.11
Silicon
Silicon is widely used as a deoxidant in steelmaking and it is often present in
quantities of 0.2-0.5%. Like nickel it encourages graphite formation and it
must therefore be kept low in high carbon steels. It dissolves in ferrite where
it has a substantial strengthening effect. Hardenability is only moderately
affected by the element. Silicon is included in some heat resisting steels in
amounts up to 1.5% as it aids high temperature resistance to oxidation.
6.3
Effect on
Effect in
Effect on
Strengthenin
Forming
Transformation
g Ferrite
Carbides
Temperatures
Manganese
Strong
Weak
Lowers
Silicon
Strong
None
Raises
Phosphorus
Strong
None
Lowers
Nickel
Moderate
None
Lowers
Chromium
Weak
Moderate
*
Copper
Moderate
None
Lowers
Molybdenum
Strong
Strong
Raises
Vanadium
Weak
Strong
Raises
Tungsten
Moderate
Strong
Raises
*
Raises or lowers depending on carbon content
Effect on
Hardenability
Strong
Moderate
Moderate
Moderate
Strong
Weak
Strong
Mild
Moderate
1.
Elements which tend to form carbides - Cr, W, Ti, V, Nb, Mo, Mn.
2.
Elements which tend to graphitise the carbide - Si, Co, Al, Ni. Elements
from category 1. should be present to avoid graphitisation when small
additions of the above are exceeded.
3.
Elements which tend to stabilise the Austenite - Mn, Ni, Co, Cu.
4.
44
7.
7.1
Weld Metal
The large number of variables inherent in welding such as the welding process
itself, the final composition of the melt, welding speed and thermal cycle make it
unrealistic even to attempt to predict with any precision the microstructures that
can arise. Nevertheless, some general points can be made. In the welding
operation itself a pool of molten metal is retained within the work piece. This
may be likened to molten metal within an ingot mould, and on freezing, large
columnar crystals will form and since the weld pool is small, and in the case of a
single arc weld, solidification rapid, they will usually occupy the complete crosssection of weld metal. This metal has a characteristic cellular-dendritic
structure of cast metal consisting of the rather coarse columnar austenitic
grains which curve into the weld centre line and a fine cellular network within
the grains. The transformation products resulting from the decomposition of
these grains is dependant mainly on the rate of cooling of the weld metal.
Although it has been pointed out that accurate predictions of weld metal
structure are not possible a schematic CCT (Continuous Cooling Time) (Fig 24)
in which general changes arising with differing cooling rates and the effects of
heat input, alloying elements and slag inclusions are related in a qualitative
way. Thus C, N, Mn etc tend to move the diagram to the right to give more time
for transformations. If cooling curves are superimposed on such a diagram it
will be clear that rapid cooling rate curves will approach the vertical whereas
slow cooling rate curves will approach the horizontal. All phases intersected by
such curves will be present in the final structure.
It may be expected that the strength and hardness of welds would be generally
high as rapid cooling rates tend to promote lower temperatures of
transformation and there are usually large quantities of impurities and alloying
elements. On the other hand the impact properties and toughness of such steel
welds can be impaired especially at the weld centre line which is the area of
maximum segregation where the columnar crystals meet. To this must be
added the deleterious effects of the coarse columnar structure with mixtures of
transformation products which may result in the precipitation of carbides which
on impact tend to rupture to produce brittle fractures of the pro-eutectoid ferrite.
45
Fig 24 Continuous Cooling Time. Schematic CCT diagram for steel weld
metal, summarising the possible effect of microstructure and alloying on
the transformation products for a given weld cooling time
In a plain carbon steel of 0.15-0.20%C with slow cooling and small undercooling below A3, a structure of blocky ferrite with pearlite will be formed. A
medium-slow cooling rate with larger undercooling below A3 will result in a form
of ferrite known as Pro-eutectoid ferrite and on further cooling the production of
ferrite needles known as Widmanstatten side plates and the remaining
austenite at even lower temperatures transforming into pearlite and cementite.
Another possible phase in such weld metals at undercooling near A1 is
Acicular Ferrite the transformation to which is enhanced by the presence of
strong carbide formers such as Mo or Cr. The presence of acicular ferrite gives
improved toughness to such welds.
The acicular ferrite is formed intragranularly resulting in randomly orientated
short ferrite needles with a basket weave feature. This interlocking nature
together with the fine grain size provides maximum resistance to crack
propagation by cleavage. Notch toughness increases with increasing volume
fraction of acicular ferrite in the weld metal. The formation of either grain
boundary ferrite, ferrite side plates or upper bainite is detrimental to weld metal
toughness since these microstructures provide easy crack propagation paths.
Medium high cooling rates result in the transformation occurring below A1 with a
fast initial ferrite growth resulting in rapid carbide concentration at the austeniteferrite interface causing the precipitation of cementite which is again followed
by very rapid ferrite growth with the same consequences. This is known as the
Periodic Pearlite reaction. A fast cooling rate results in the formation of the
phase Upper Bainite, while a very fast cooling rate may produce Lower
Bainite or Lath martensite.
46
7.2.
The thermal cycle that is to say the heating time, the time at temperatures or
dwell time, and the cooling time are important and must be considered together
with the presence of precipitates and their solubility at high temperatures.
Moreover the previous thermal and mechanical history is also important. Thus
for example the original steel may have been in the cold rolled condition, it may
have been annealed or normalised or subjected to other treatments. With
these aspects in mind the sub-zones may be considered separately since each
one will have a different type of microstructure with appropriately different
properties. Notwithstanding the complexities involved such structure can be
predicted with greater certainty then those arising in the weld metal.
7.3
48
7.4
A weldable structural steel will normally have a CE value not greater than
0.40%. Other formulae such as PCM used in Japan are also available. It should
be realised that such formulae and the values calculated from them are
principally guides and circumstances may arise when departures from them are
justified.
Essentially a Carbon Equivalent is a measure of the hardenability of a steel.
49
8.
STRUCTURE OF INGOTS
When molten metal is poured into a metal ingot mould, solidification will usually
begin with the formation of small chill crystals at the mould-metal interface (Fig
26). These are followed by long columnar crystals growing at right angles to
the mould surface. The size of these crystals will depend on the rate of
solidification and they will be small if this is rapid, increasing in size with slower
rates. With very slow solidification, as with a sand mould for example, the
columnar and chill crystals will not generally form but dendrites will develop into
irregular equi-axed grains. Where columnar crystals have formed, planes of
weakness can be expected at sharp corners and in extreme cases even at the
ingot centre.
Pipe
As a layer of cooled metal forms around the ingot walls, contraction occurs
resulting in a fall of the level of liquid. Successive layers of solid form, each
accompanied by a fall in the liquid level, the fall increasing as the volume of
liquid decreases. In this manner a central cavity is formed, known as Primary
Pipe. With the ingot mould designed narrow end up (Fig 27) a conical
volume of metal still remains liquid after the top portion of the ingot is solid.
Solidification of this metal will give rise to further cavities known as Secondary
Pipe.
50
Segregation (fig.28)
Molten steel contains soluble impurities - sulphur and phosphorus - and soluble
alloying elements together with insoluble impurities or slag particles in
suspension. The first crystals to separate contain less impurity than the average
composition and those elements which lower the freezing point, such as
sulphur, phosphorus, carbon, silicon and manganese collect in the last portions
to solidify. This phenomenon is known as segregation and in the case of steel
ingots means that there is a concentration of sulphur, phosphorus and carbon in
the centre and upper portions of the ingot. Associated with the pipe they are
largely removed when it is discarded.
Segregation also occurs as the microscopic scale. Impurities and soluble
alloying elements are rejected by the solidifying crystal with the result that an
alloy rich area surrounds each crystal. This can be clearly seen in carbon steel
castings, the original crystal lower in alloy content tends to be ferritic whilst the
more highly alloyed crystal surround is pearlitic.
51
Steel Types
Steel, manufactured from impure pig-iron or scrap, is first purified to a great
extent by a process of oxidation which inevitably leaves the molten material with
excessive oxygen which must be reduced to render it suitable for casting to an
ingot. The steel type is defined by the degree of deoxidation.
52
53