ALLOY,STEEL,SOLIDIFICATION

MODULE 2

MECHANICAL
ENGINEERING
SUMA.B.T VANISHREE T S

SJB
I N S T I T U T E O F T E C H N O LO G Y
CHAPTER 1

Alloy

An alloy is a combination of metals or of a metal and another element. Alloys are defined by a metallic bonding character.[1] An alloy may be a solid solution of metal elements (a single
phase) or a mixture of metallic phases (two or more solutions). Intermetallic compounds are alloys with a defined stoichiometry and crystal structure. Zintl phases are also sometimes
considered alloys depending on bond types (see also: Van Arkel–Ketelaar triangle for information on classifying bonding in binary compounds

Alloys are used in a wide variety of applications. In some cases, a combination of metals may reduce the overall cost of the material while preserving important properties. In other cases,
the combination of metals imparts synergistic properties to the constituent metal elements such as corrosion resistance or mechanical strength

1
Examples of alloys are steel, solder, brass, pewter, duralumin, bronze and amalgams.
The alloy constituents are usually measured by mass percentage for practical applications,
and in atomic fraction for basic science studies. Alloys are usually classified as
substitutional or interstitial alloys, depending on the atomic arrangement that forms the
alloy. They can be further classified as homogeneous (consisting of a single phase), or
heterogeneous (consisting of two or more phases) or intermetallic.
An alloy is a mixture of chemical elements, which forms an impure substance (admixture)
that retains the characteristics of a metal. An alloy is distinct from an impure metal in that,
with an alloy, the added elements are well controlled to produce desirable properties, while
impure metals such as wrought iron are less controlled, but are often considered useful.
Alloys are made by mixing two or more elements, at least one of which is a metal. This is
usually called the primary metal or the base metal, and the name of this metal may also be
the name of the alloy. The other constituents may or may not be metals but, when mixed
with the molten base, they will be soluble and dissolve into the mixture. The mechanical
properties of alloys will often be quite different from those of its individual constituents. A
metal that is normally very soft (malleable), such as aluminium, can be altered by alloying it
with another soft metal, such as copper. Although both metals are very soft and ductile, the
resulting aluminium alloy will have much greater strength. Adding a small amount of
non-metallic carbon to iron trades its great ductility for the greater strength of an alloy called
steel. Due to its very-high strength, but still substantial toughness, and its ability to be
greatly altered by heat treatment, steel is one of the most useful and common alloys in
modern use. By adding chromium to steel, its resistance to corrosion can be enhanced,
creating stainless steel, while adding silicon will alter its electrical characteristics, producing
silicon steel.
Properties of Alloy
Various alloys have different properties like strength, malleability, visual attractiveness etc.
Copper and tin uses to make Bronze, an important alloy harder than copper. This quality has
been utilized for imprint the civilization and history of mankind for thousands of years
called bronze age. In our daily life, mankind uses alloys in almost all of the fields that uses
metals. Most known elements have involvement in making alloys thus we have tens of
thousands of alloy products. Alloys are attractive due to its improved quality for make
utilizing the pure elemental metals.
How to make Alloy?
2
Alloys can be made by combining two or more metal elements while in a molten state or by
bonding metal powders. Various alloys have different desired properties such as strength,
visual attractiveness, or malleability. The number of possible alloy combination is almost
endless since any metal can be alloyed in pairs or in multiples. Some alloys have hardness
while some have low melting points and some others have better magnetic or electrical
characteristics; some have high corrosion resistant.
These occurs due to changes happened in the internal and external characteristics during the
process of making alloys. Corrosion-resistant alloys are readily formed and joined using
conventional techniques and equipment. Solid solution alloy products are normally used in
the annealed condition.
Age-hardenable alloys are best fabricated in the annealed condition and either directly aged
or annealed and aged afterward to achieve high strength. Corrosion-resistant alloys are
normally formed at room temperature. If severe deformation is required, it may be necessary
to either use multiple deformations with annealing performed between operations or the part
may be heated to an elevated temperature at which greater deformation is possible.
After hot forming, parts should be annealed to restore corrosion resistance. In most cases,
cold-formed components may be placed in service without annealing. However, if the
environment is such that it might induce stress corrosion cracking, the cold-formed parts
should be annealed. Age-hardened alloys are not normally used in environments that can
induce stress corrosion.
Different Types of Metal Alloys
Bearing alloys: It is being used for accommodating enough pressure under sliding contact
with another metal body commonly known as rotating shaft of the motor, generator, vehicles
and various types of propellers.
Corrosion-resisting Alloys: Noble metal uses to make corrosion-resistant alloys which
initially oxidized and act as separation layer preventing chemical action from other materials
or corrosive environment. Stainless steel and aluminum alloy are examples of these alloys.
Super-Austenitic Stainless Steels Alloy (SASS Alloy): During the last decades of the 20th
century, stainless steel technology took a giant leap forward with the development of higher
nickel stainless steels enhanced by the addition of nitrogen for improved strength and
corrosion resistance. These alloys normally contain about 6% molybdenum, so they offer
excellent resistance to localized corrosion in reducing and mixed acid environments. They
contain sufficient chromium for resistance to oxidizing environments as well.
High-Strength Corrosion-Resistant Alloys: offers corrosion-resistant alloys that are
essentially precipitation-hardenable (age-hardenable) versions of their solid-solution
counterparts. These products offer the corrosion resistance of the standard alloys but more
than twice the strength. In addition, precipitation-hardenable alloys can be fabricated prior to
heat treatment when they are relatively soft and ductile and then heat treated afterword to
develop high strength.
Other alloys are Dental alloy and Die-casting alloy which are widely used in our daily life.
Steel Alloys
Combining iron and a small amount of carbon gives variety of steel products. To make
different quality of steel alloys, we add molybdenum, nickel, silicon, boron and manganese.
Factors affecting solubility
Temperature
Basically, solubility increases with temperature. It is the case for most of the solvents. The
situation is though different for gases. With increase of the temperature they became less
soluble in each other and in water, but more soluble in organic solvents.
Polarity
In most cases solutes dissolve in solvents that have a similar polarity. Chemists use a
popular aphorism to describe this feature of solutes and solvents: "Like dissolves like".
Non-polar solutes do not dissolve in polar solvents and the other way round.
Pressure
Solid and liquid solutes
For majority of solid and liquid solutes, pressure does not affect solubility.
Gas solutes
As for gasses the Henry's law states that solubility of gas is directly proportional to the
pressure of this gas. This is mathematically presented as: p = kc, where k is a temperature
dependent constant for a gas. A good proof of Henry's law can be observed when opening a
bottle of carbonated drink. When we decrease the pressure in a bottle, the gas that was
dissolved in the drink bubbles out of it.
3
Molecular size
The larger the molecules of the solute are, the larger is their molecular weight and their size.
It is more difficult it is for solvent molecules to surround bigger molecules. If all of the
above mentioned factors ale excluded, a general rule can be found that larger particles are
generally less soluble. If the pressure, and temperature are the same than out of two solutes
of the same polarity, the one with smaller particles is usually more soluble.
Stirring increases the speed of dissolving
Stirring does not have an affect on solubility of a substance, but everyone knows that if he
puts sugar in his tea and does not stir, it will not dissolve. Actually, if we left the tea to stand
for a long enough time, the sugar would dissolve. Stirring only increases the speed of the
process - it increases move of the solvent what exposes solute to fresh portions of it, thus
enabling solubility. As molecules in liquid substances are in constant move, the process
would take place anyway, but it would take more time.
Hume-Rothery rule
While developing an alloy, it is frequently desirable to increase the strength of the alloy by
adding a metal that will form a solid solution. Hume-Rothery has framed empirical rules that
govern the choice of alloying elements in the formation of substitutional solutions. We may
note that if an alloying element is chosen at random, it is likely to form an objectionable
intermediate phase instead of a solid solution. Extensive solid solubility by substitution
occurs, when
(i) the solute and solvent atoms do not differ by more than 15% in size, i.e. diameter.
Within this limit of size factor, each of the metals will be able to dissolve appreciably (to the
order of 10%) in the other metal. However, if the atomic size factor is greater than 15%,
solid solution formation tends to be severely limited and is usually only a fraction of one
percent.
(ii) the electronegativity difference between the elements is small. If the chemical
affinity of two metals is greater, then the solid solubility will be more restricted. When the
chemical affinity of two metals is great, they tend to form an intermediate phase rather than
a solid solution.
(iii) the valency and the crystal structures of the elements are the same. If the alloying
element has a different valence from that of the base metal, the number of valence electrons
per atom (called the electron ratio), will be changed by alloying. We may note that the
crystal structures are more sensitive to a decrease in the electron ratio than to an increase.
Obviously, a metal of high valence can dissolve only a small amount of lower valence metal;
whereas the lower valence metal may have good solubility for a higher valence metal.
Moreover, only metals that have the same type of lattice (for example FCC) can form a
complete series of solid solutions. For complete solubility, it is found that the size factor
must usually be less than 8%. Examples of binary and ternary systons exhibiting complete
solid solubility are Cu-Ni and Ag-Au-Pt respectively.
Ag-Au, Cu-Ni and Ge-Si are the systems which satisfy Hume Rothery conditions very well
(Table ).
Obviously, these systems form complete solid solutions, i.e. the elements mix in each other
in all proportions.
Binary Phase Diagrams
Before any calculations can be made a tie line is drawn on the phase diagram to determine
the percent weight of each element; on the phase diagram to the right it is line segment LS.
This tie line is drawn horizontally at the composition's temperature from one phase to
another (here the liquid to the solids). The percent weight of element B at the liquidus is
given by wl and the percent weight of element B at the solidus is given by ws. The percent
4
weight of solid and liquid can then be calculated using the following lever rule equations:
where two is the percent weight of element B for the given composition.
The numerator of each equation is the original composition we are interested in +/- the
Opposite lever arm. That is if you want the percent weight of solid then take the difference
between the liquid composition and the original composition. And then the denominator is
the overall length of the arm so the difference between the solid and liquid compositions.
Eutectic Phase Diagrams
There is now more than one, two phase region. The tie line drawn is from the solid alpha to
the liquid and by dropping a vertical line down at these points the wt% of each phase is
directly read off the graph, that is the percentage weight of the x axis element. The same
equations can be used to find the total percentage of alloy in each of the phases, i.e. Xs is the
percentage of the whole sample in the liquid phase
the following about reading the diagram:
1. The liquidus line separates the all melt phase from the melt+crystal phase.
2. The solidus line separates the melt+crystal phase from the all crystal phase.
NOTE that the solidus and liquidus lines are experimental, they have been determined by
melting and cooling many melts at different percent compositions.
3. The eutectic is the point at which all three phases can exist simultaneously, A, B, and
melt. The eutectic here is 50% B, but can be any percent depending on the minerals
involved.
Eutectoid System
When the solution above the transformation point is solid, rather than liquid, an analogous
eutectoid transformation can occur. For instance, in the iron-carbon system, the austenite
phase can undergo a eutectoid transformation to produce ferrite and cementite, often in Lever Rule
lamellar structures such as pearlite and bainite
The lever rule is a tool used to determine weight percentages of each phase of a
binary equilibrium phase diagram. It is used to determine the percent weight of liquid and
solid phases for a given binary composition and temperature that is between

the liquidus and solidus.In an alloy with two phases, α and β, which themselves contain two
elements, A and B, the lever rule states that the weight percentage of the α phase is

where

• a is the weight percentage of element B in the α phase

• b is the weight percentage of element B in the β phase

• c is the weight percentage of element B in the entire alloy

all at some fixed temperature.

5
SECTION 1

Solidification

SOLIDIFICATION
FUNDAMENTALS OF SOLIDIFICATION PROCESS
Solidification is one of the most important phase transformations in materials, and its
proper understanding is essential in control of many fabricating processes. The
transformation of a metal from the liquid to the solid state is often called primary
crystallization.
Solidification proceeds owing to the conversion of matter to a more stable thermodynamic
state with less free energy E. Free energy is reversibly changed upon changes in
temperatures, allotropic transformations, fusion (melting) etc. At temperature Ts amount of
free energies are equal in the liquid and in solid state. This is the equilibrium temperature of
solidification (or melting) of the substances of which both phases (liquid or solid) may exist
simultaneously.

6
 At temperature above Ts, liquid metal is more stable having less that lower temperatures
solid metal is more stable. The solidification process proceeds only when there is a
difference in the free energy as a result of lesser free energy of solid metal in comparison
with that in the liquid state .Therefore, solidification is initiated and proceeds only when the
metal is supercooled below the equilibrium temperature Ts of solidification. The difference
between the temperature Ts and temperature Tc at which solidification

proceeds under given conditions is called the degree of supercooling Ts – Tc

Fig shows the cooling curve for a pure metal. This is a schematic illustration of the
temperature of metal in a container in which the metal is initially molten (i.e., entirely
liquid) when heat is removed at constant rate. As heat is removed, the temperature of the
melt decreases with time until some temperature below the melting (or freezing) point is
reached at that time; there is a change of curvature. The temperature rises to the melting
point, remains at this temperature for some time and then decreases rapidly.

Solidification of pure metals is considered to take place in two stages namely nucleation and
crystal growth. Nucleation

It is seen that the atoms are not chaotically arranged in a liquid metal as they are in the
gaseous state; but at the same time they do not have the regular orderly characteristic of a
solid (crystal) body.

7
At a temperature somewhat lower than Ts (melting temperature), micro volumes having
atomic arrangement similar to that in the solid metal acquire higher stability and become
centers of crystallization (nuclei or embryos). creation of solid – liquid interface decreases as r3 increases. However the retarding force,
which is the surface energy, increases as r2 increases.
Nuclei of a great variety of size appear during the solidification process. Not all nuclei,
however are capable of further growth. This is due to the fact that the free energy of the Fig shows a plot of free energy versus the embryo radius r. the maximum equal to * is
system is reduced in solidification when a certain volume of the reached for r=rc where rc is the critical radius of the embryo.at the critical radius, the
increased owing to the formation of an interface with which a certain volume free energy decreases, just equals the surface free energy of the
amount of free energy is associated. Nucleation may occur by two
nucleus.
mechanisms namely homogeneous nucleation and heterogeneous
nucleation. Differentiating
equation (1) with
Homogeneous nucleation
respect to r and
In homogeneous nucleation the stability of a nucleus is controlled by two factors (i) the free equating it to zero,
energy change during the liquid – solid transition, and (ii) the value of the surface energy of will give
the nucleus thus formed. At temperature, below the melting temperature Ts, 0 is negative,
and hence the first term on the right of equation (1) is negative. Since is always positive the
second terms representing the surface energy between the embryo, and the matrix is
positive. For a spherical embryo the term (FORMULA),which is the driving force for the
When r>rc the free energy of the system decreases initiating the formation of crystal.

It is seen that upon the formation of a nucleus of a size less than the critical value rc, the free
energy of the system increases because the increment of free energy due to the formation of
a new interface exceeds reduction in free energy due to the formation of a nucleus of solid
metal. Therefore a nucleus of a size less then rc cannot grow and soon dissolve in the liquid
metal. If a nucleus appears with a size exceeding rc, it will be stable and will be capable of
growth because the free energy of the system reduces as the size of the nucleus increases.

Heterogeneous nucleation

Variation of free energy with the radius of a nucleus

8
Most frequently, the source about which nuclei are formed on solid particles are always
present in the melt. If the particles of the impurity have a crystal lattice of a structure more
or less closely resembling that of the solidifying metal, then they play the part of ready
centers of crystallization. Such surfaces or impurities are ―wetǁ by both liquid and solid
lowering the net energy associated with the formation of nucleus. Fig ( ) illustrates
mechanism of heterogeneous nucleation. The heterogeneous nucleus is considered as a
spherical cap on a solid, flat substrate. The volume of the cap depends on the contact
angle at the nucleus – liquid- substrate junction. If the contact angle is less than 180 a
particular surface will serve as nucleation catalyst for that system. The change in free energy
associated with the formation of the embryo is given by,
Where V =volume of the spherical cap (nucleus). AcL =the interfacial surface
area between liquid and the cap. r =the radius of the cap (nucleus)
CL, SC and SL are interfacial surface tension between Cap (nucleus) liquid, cap
substrate and substrate liquid respectively. In homogeneous nucleation, the critical size of
the nucleus given by
and it is independent of contact angle. In heterogeneous nucleation, however, the value of
CL, the interfacial surface tension, is much smaller, therefore the critical size of the nucleus
will be much smaller. As a result, the number of atoms that must be crystallized
before the critical radius size rc is reached is much less for heterogeneous nucleation than
for the homogeneous one, and hence smaller amount of undercooling is required.
CRYSTAL GROWTH
A nucleus grows as a result of the transfer of atoms from the super cooled liquid to the
crystal Crystals grows in layers of a single atom thickness.
9
In general it grows most rapidly in the directions that are most densely packed with atoms,
since these offer positions of exceptionally low energy to unknown atoms from the melt.
The usual result is the development of skeleton crystal built up of branching arms, each of
which represents a specific crystallographic direction along which growth is rapid. As long
as each crystal remains completely isolated from other crystal, its geometry remains almost
perfect. Eventually in their growth individual crystals approach each other closely and
complete for the last unattached atoms, which constitute the thin layer of molten metal
remaining between them. In this competition they interfere mutually. The last stage of
growth, occurring by the chance accretion of liquid atoms to one or the other of these
crystals is corresponding erratic. Finally, when solidification is complete, little evidence of
plane faces remains. Typically the solid metal consists of crystals which are rough, very
irregular polyhedral.
In their external forms such crystals reflect little of their remarkable internal symmetry and
so they are often called grains or crystallites instead of crystals .Occasionally, these grains
are equiaxed, that is substantially equal in their three dimensions, more commonly they are
dendritic, that is elongated in a specific crystallographic direction along which growth was
outstandingly rapid. Sometimes they show well developed branching structure. Their sizes
in any given case depends directly upon the number of several variables but principally on
the cooling rate. Under various conditions of freezing, the
crystals may be so fine that they are unresolvable by an optical microscope, or they may
range upwards in size to rare crystals of the size of a man‘s hand.
THE CAST METAL STRUCTURES
The given structure of the cast metals depends on the number of nuclei formed during
solidification. When only few nuclei are formed, then a coarse or a large grain structure is
obtained. When the number of nuclei formed is large, a fine grain structure results.
Generally, a fine grained structure is preferred in cast metals because it results in mechanical
strength.
When a pure metal is cast in a stationary mould (without the presence of impurities), the
types of structures obtained are classified as,
1. Chilled grains.
2. Columnar grains.
3. Equiaxial grains.
Depending on the number of nucleating sites available and the cooling rate, the above grain
structures may appear individually or in any combination. Fig shows a typical cast metal
structure containing all the three types of grains (assuming no shrinkage).
Consider a hot liquid metal poured into a cool metallic mould. The layer, of the liquid next
to the mould wall cools immediately. As the cooling rate is very, high nucleation is rapid,
and many grains grow. However their growth is restricted because of their large numbers.
This zone of grain is called ‗chill zone‘. Here the grains are equiaxed that is they have
nearly same dimensions along the three major axes.
The solidification proceeds in the inner layers where the temperature is decreasing. As the
chill zone grows thicker, the temperature gradient from the liquid becomes less steep which
makes the liquid next to this shell to cool more slowly, with less undercooling. The grains
formed in this region, tend to grow inward forming longer grains directed away from the
chill zone. This zone is called the columnar zone. In most metals and alloys, columnar
crystals grow as cellular dendrites.
The growth of columnar grains continues until they meet the dendritic structures of the
grains growing at the center of the mould. The central grains from nuclei formed at the
center develop into larger Equiaxial grains. The Equiaxial grains at the center are larger than
those at the chill zone. To produce equiaxed grains throughout the casting, nucleants may be
added to the liquid metals. In such case, solidification starts with heterogeneous nucleation.
10
Phase diagrams
The characteristic of any series of alloys can be easily studied by using alloy
phase diagrams. A phase diagram is a graphical description of the kinds and amounts of the
phases that can be expected in an alloy as a function of its composition, temperature, and
pressure, when it has reached thermodynamic equilibrium.
The phases may be liquid, vapour or solid with various ordered and disordered crystal
structures. A phase diagram does not provide information about how rapidly equilibrium can
be reached. When a phase diagram is determined experimentally, it is necessary not only to
find out what phases are present but also to assure that the alloy is in the stable equilibrium
state. Equilibrium is reached when the Gibbs free energy of the system has reached its
lowest possible value. The thermodynamic principle of minimum Gibbs free energy imposes
restrictions on the possible forms a phase diagram can take, and even a complicated diagram
with many phases is composed of only a few geometrical features. The following terms are
frequently used in the study of solid phases and phase diagrams:
(i) System: A system may be composed of solids, liquids, gases or their combinations
and may have metals and non-metals separately or in any combination. It is explained as the
whole complex of phases of one or several components at different pressures and
compositions. A system is so isolated from its surroundings that it is unaffected by solids,
liquids, gases or their combinations and is subjected to the change in the overall
composition, temperature, pressure or total volume, only to the extent permitted by the
investigator.
(ii) Components: These are the substances, either chemical elements or chemical
compounds, whose presence is essential and sufficient to make a system. A pure metal is
called a onecomponent system, an alloy of two metals is called a binary or two component
system, etc. (iii) Phase: It is a homogeneous portion of a system that has uniform physical
and chemical characteristics. The number of phases in a system is the number of different
substances that exist in it in a homogeneous system.
(iv) Phase diagram: A graphical representation of the relationships between
environmental constraints (e.g. temperature and sometimes pressure), composition, and
regions of phase stability, ordinarily under conditions of equilibrium. Most phase diagrams
are prepared by using slow cooling conditions whereby phases are in equilibrium. One can
get following important informations from the phase diagrams

(a) Phases at different composition and temperature (b) Equilibrium solubility of one
element or compound in another element. (c) Melting points of different phases in an alloy.
(d) Temperature of solidification or range of solidification of an alloy.

(v) Phase Equilibrium: The state of a system where the phase characteristics remain
constant over indefinite time periods. At equilibrium the free energy is a minimum. In an
equilibrium diagram, liquid is one phase and solid solution is another phase.

(vi) Phase Transformation: A change in the number and/or character of the phases that
constitute the microstructure of an alloy.

11
SECTION 2

Solid Solution

Solid solution

A solid solution forms when, as the solute atoms are added to the host material, the crystal
structure is maintained, and no new structures are formed. In other words, when elements
completely dissolve in each other in liquid and or solid state the resulting phase is called
solid solution. Solid solutions form readily when solvent and solute atoms have similar
sizes and electron structures, so that it is compositionally or chemically homogeneous and
the component atoms of the elements cannot be distinguished physically or separated
mechanically. There is a homogeneous distribution of the constituents in the solid state so
as to form a single phase or solid solution.
Basically, solid solutions are of two typesSubstitutional Solid Solution When the two
metals in solid solution form a single face centred cubic lattice, i.e., in general solute or
impurity atoms replace or substitute for the host atoms, is called as substitutional solid
solution. One may also define solid solutions as crystalline phases of a variable
composition
Atoms of a solute B can be arranged in the crystal lattice of a solvent A either by
substituting for some atoms of the latter in the crystal lattice or by occuping the interatomic

12
spaces between atoms, or interstices. We may note that the atoms of the two metals be of
almost same size,i.e., the difference in atomic radii between the two atom types be less than
about _15%. Otherwise the solute atoms will create substantial lattice distortion and a new
phase will form. For appreciable solid solubility the crystal structures for metals of both
atoms must be same. If one element has more electropositivity and the other more
electronegativity, then there is greater likelihood that they will form an intermetallic
compound instead of a substitutional solid solution. It is also observed that other factors
being equal, i.e. atomic size, crystal structure and electronegativity, a metal will have more
of a tendency to dissolve another metal of higher valency than one of a lower valency. A
familiar example of substitutional solid solution is found for copper and nickel to form
monel. These two elements are

completely soluble in another at all proportions. Brass, an alloy of copper and zinc, is
another example, which forms solid solutions most readily as the atoms of these two
elements have similar sizes and electronic structure unlimited solubility in the solid state can
be observed in copper-gold, and germanium-silicon alloys. Polymorphous metals may
possess unlimited solubility within a single modification of the space lattice. For example,
Feα can form a continuous series of solid solutions with Cr (BCC lattices) and Feϒ , a
continuous series of solid solutions with Ni (FCC lattices). The formation of solid solutions
is always associated with an increase of electric resistance and decrease of the temperature
coefficient of electric resistance. Solid solutions are usually less plastic (except for
copperbased solid solutions) and always harder and stronger than pure metals.
a)Substitutional solid solution
Substitutional solid solutions are of two types:
(i) Random substitutional solid solutions and (ii) Ordered substitutional solid solutions.
When there is no order in the substitution of the two metal elements, the chance of one metal
element occupying any particular atomic site in the crystal is equal to the atomic percent of
the element in the alloy. Obviously, in such a situation the concentration of solute atoms can
vary considerably throughout the lattice structure. Such type of the resulting solid solution is
called a random or disordered substitutional solid solution.
Many substitutional solid solutions can be in an ordered state at relatively low temperatures,
i.e. unlike atoms of two elements are distributed between the sites of the space lattice not
statistically, but in a perfectly definite order. Such solid solutions are called ordered; the
term superstructure‘ is also in use. Such ordering is common at low temperatures because
greater thermal agitation tends to destroy the orderly arrangement.
The change from a disordered to ordered state takes place at a definite temperature or in a
definite temperature range. The temperature at which a solid solution becomes completely
disordered is called the Kurnakov point (ϴ K). Ordering usually takes place under the
conditions when a solid solution is cooled slowly from the temperature region above ϴ K.
Ordered solid solutions can be found in systems with either substantial or unlimited
solubility in the solid state; in that case complete ordering can occur with concentrations of
the solid solution elements corresponding to simple atomic ratios of the components of the
type, say AB or AB3. Partial ordering may be observed in systems with concentration ratios
close to the indicated ones. The arrangement of atoms in ordered solid solutions of two Cu
and Au alloys of the
corresponding to AuCu3
crystal lattice of Cu-Au alloy
and AuCu are shown in
Fig.

The appearance and

disappearance of an order
in the arrangement of

13
atoms in solid solutions is associated with changes in the properties of an alloy. Ordering
increases the electrical conductivity, temperature coefficient of electric resistance, hardness,
and strength, but decreases the ductility of an alloy. In ferromagnetic alloys, it changes
magnetic properties; for instance, the magnetic permeability of perm alloys (magnetic
iron-nickel alloys) can drop on ordering to a small fraction of the original value. Some
alloys are paramagnetic in disordered state, but become ferromagnetic after ordering, such
as Heusler (Mn-Cu-Al) alloys. Usually, substitutional solid solutions have a random
arrangement of the constituent atoms on the atomic sites, especially at elevated
temperatures. This is so, as configurational entropy makes a greater contribution
in lowering the free energy with increasing temperature, as we have G = H – TS. This
random arrangement of the constituent atoms in a solid solution may change over to an
ordered arrangement on cooling to lower temperatures, if ordering lowers the enthalpy of the
crystal sufficiently.
(b) Interstitial Solid Solutions These can form, for instance, on melting together
transition metals and non-metals with a small atomic radius (H, N, C or B). The possibility
of obtaining an interstitial solution is mainly determined by the size factor; i.e., the size of a
solute atom must be equal to or slightly smaller than the size of an interstitial void.
Interstitial solid solutions always have a limited solubility and form preferably in solvents
having an HCP or FCC lattice with interstices of a radius of 0.41 R, where R is the radius of
a solvent atom. In
BCC lattices, the solubility is low, since the size of interstices does not exceed 0.29 R.
Examples of interstitial solid solutions of commercial application are solid solution of
carbon in Feα , and Feϒ , Fer, which has an FCC lattice, can dissolve upto 2.14% (by mass)
of carbon; Fe_ (BCC lattice) does not practically dissolve carbon, the maximum solubility
being around 0.02 (by mass). Other elements like: nitrogen for maintaining stainless steel in
austenitic condition for nitriding condition and hydrogen when introduced into steels during
welding operations, acid cleaning and plating results in hydrogen embrittlement and causes
a sharp decrease in ductility.
Lattice distortions appearing on the formation of interstitial solid solutions are stronger than
those in the substitutional solid solutions, because of which the properties of alloys can be
changed more drastically. As the concentration of a solute in a solid solution increases, this
increases noticeably the electric resistance, coercive force, hardness and strength, but
decreases the ductility and toughness. Interstitial solid solutions usually have very limited
solubility and are normally considered of secondary importance.
14
Alloys containing more than two elements can form either substitutional or interstitial
solution. For example, when iron is melted together with manganese and carbon, manganese
and iron form substitutional solid solution while carbon and iron, interstitial solid solution.
In conclusion we can say that solid solutions are crystals whose properties are close to those
of the solvent, since they retain the same crystal lattice and type of bond. In particular, solid
solutions of metals are distinguished by high plasticity: they are readily deformable in the
hot state and many of them, in the cold state. Solid solutions are the bases of most
commercial structural and special alloys.
Phase rule – Gibbs phase rule
This expresses mathematically the general relationships for the existence of stable phases
corresponding to the equilibrium conditions. It enables us to predict and check the processes
that occur in alloys during heating or cooling. Using this rule, it is possible to determine
whether the solidification process takes place at a constant temperature or within a certain
temperature interval; it can also indicate the number of phases that can exist simultaneously
in a system.
The phase rule enunciated by J.W. Gibbs relating number of phases P, number of
components C, and number of degrees of freedom F has a simple form:
P+F = C + n (1)
P+F = C+2
n = number of external factors = 2 (temperature and pressure)
In applying the phase rule to metal systems the effect of pressure is neglected, leaving only
one variable factor,—temperature. Equation (1) reduces to
F = C + 1 – P 1(a)
The number of degrees of freedom is essentially the number of independent variables, both
internal (composition and phases) and external ones (temperature, pressure, concentration
etc.), which can be changed without changing the number of phases in equilibrium. The
number of indepenent variables cannot be more than the number of variables, i.e.
F = C – P + 2 _ P(C – 1) + 2 (2)
where P(C – 1) denotes the total number of compositional variables when P phases are there
in the system.
Including the two external variables (pressure and temperature), the total number of
variables is P(C – 1) + 2.

In equilibrium all factors have definite values, hence the degrees of freedom cannot be less
than zero, C – P + 1 _ 0 then P _ C + 1 Obviously, the number of phases in a system cannot
exceed the number of components plus one. The components of a system may be elements,
ions or compounds. The components refer to the independent chemical species that comprise
the system. In the ice-steam system, the component is H2O, in the Cu-Ni system the
components are the elements Cu and Ni, whereas in the Al2O3-Cr2O3 system, one can take
the two oxides to be components. In the Fe-C system, although Fe and graphite can be taken
as components, but it may be convenient to choose Fe and Fe3C (iron carbide) as the
components.

As follows from the phase rule, the number of phases existing simultaneously in a binary
system cannot be more than three. These three phases can only exist at a definite phase
composition and a definite temperature. If the number of phases in a binary system turns out
to be more than three, this means that either the alloy is not in the equilibrium state or the
number of phases and constituents has been determined incorrectly. In a ternary system no
more than four phases may be in equilibrium. When only one phase is present in a system,
the degrees of freedom are equal to the total variables, with the increase in number of
phases, the degrees of freedom decrease. The degree of freedom cannot be less than zero.
Obviously, we have an upper limit to the number of phases that can exist in equilibrium in a
given system. At solidification temperature, a pure metal is a one- component system
Iron-Carbon (Cementite) diagram
consisting of two phases of identical composition F = 1 + 2 – 2 = 0 Clearly, the number of
There is more to the iron-carbon phase diagram than related in the backbone. In particular,
phases and number of degrees of freedom equals zero, i.e. F = 0. This is known as
there is some nomenclature that I avoided in the main text but that is important for
non-variant equilibrium. When the number of phases is less than the maximum possible
understanding other writings about iron and steel. So let's start with a phase diagram that
number by one, the number of degrees of freedom will also increase by one (F = 1). Such
contains maximal information
type of system is called as monovariant.

An alloy of two metals is a two-phase and two-component system at solidification, F = 1.

When F = 2, the system is said to be a divariant. Obviously, a system may be in equilibrium The important boundaries (the lines) separating phases have some universally used
at different temperatures and concentrations. abbreviations:

One can represent all transformations occurring in alloys and depending on temperature and
concentration (C = 2) by equilibrium diagrams. The equilibrium diagrams are plotted with
concentration as the abscissa and temperature as ordinate.

15
 Lorem ipsum
Iron dolordiagram
carbon sit amet, consectetur adipisicing elit, sed do tempor
incididunt ut labore et dolore magna aliqua.
•A1: The upper limit of the ferrite / cementite phase field (horizontal line going
through the eutectoid point).

• A2: The temperature where iron looses its magnetism (so-called Curie
temperature). Note that for pure iron this is still in the a-phase.

• A3: The boundary between the g austenite and the austenite/ ferrite field.

• A4: The point in this case where a changes to d at high temperatures.

• ACM: The boundary between the g austenite and the austenite / cementite
field.

16
Keynote on Iron carbon diagram

17
Question 1 of 5
how many components are present in binary phase system?

A. 6

B. 4

C. 2

D. 8

Check Answer

18
Crystallization
Crystallization is also a chemical solid–liquid separation technique, in which mass transfer of a solute from
the liquid solution to a pure solid crystalline phase occurs. In chemical engineering, crystallization occurs in
a crystallizer.

Related Glossary Terms

Drag related terms here

Index Find Term

Chapter 1 - Solidification
Crystallized
form or cause to form crystals.

Related Glossary Terms

Drag related terms here

Index Find Term

Chapter 1 - Solidification
Precipitation
In meteorology, precipitation is any product of the condensation of atmospheric water vapor that
falls under gravity. The main forms of precipitation include drizzle, rain, sleet, snow, graupel and
hail.

Related Glossary Terms

Drag related terms here

Index Find Term

Chapter 1 - Alloys, Steels, Solidification

Steel Alloys

Alloy steels contain alloying elements (e.g. manganese, silicon, nickel, titanium, copper, chromium, and aluminum) in varying
proportions in order to manipulate the steel's properties, such as its hardenability, corrosion resistance, strength, formability,
weldability or ductility.

Related Glossary Terms

Drag related terms here

Index Find Term

Chapter 1 - Alloys, Steels, Solidification

Substitutional solid solution

Substitutional solid solution strengthening occurs when the solute atom is large enough that it can replace solvent atoms in their
lattice positions. Some alloying elements are only soluble in small amounts, whereas some solvent and solute pairs form a
solution over the whole range of binary compositions.

Related Glossary Terms

Drag related terms here

Index Find Term

Chapter 1 - Solid Solution