Chapter 2 - Classification, Structure and Solidification of Materials

Four states of matter: Gas , liquid , solid and plasma

The GASEOUS STATE is the state of matter that has no resistance to change of shape.

The LIQUID STATE is a state of matter where the materials have fixed volume but assume the shape of the
container in which they are placed.

There are at least four different mechanisms by which the atoms can assume positions well fixed enough that for
practical purposes the material could be called SOLID.

PLASMA which is typically an ionized gas is considered a separate phase from gas because it has one or more
free electrons which are not bound to the atom and thus the material is electrically conductive.
 All metals occur as crystalline solids.

Definition of a metal- Materials having some degree of plasticity, relatively high hardness and strength, good electric conductivity and crystallinity when solid.

Basic properties of metals are:

- metals tend to be good conductors of electricity and heat.
- they are often malleable, (they can be extensively deformed without fracture at room temperature
and at high strain rates.
- they are hard and strong at room temperature.
- metals cannot be made transparent, unless the metal is thin.
- they can be made stronger or tougher by thermal and chemical treatments as well as mechanical
strengthening methods.
- some metals have desirable magnetic properties.
- metals can be re-melted and recycled.
 CERAMICS

Ceramics are most frequently composed of compounds of metal and nitrogen or compounds of
metal and carbon.

Properties of ceramics are:

- they are electrical and thermal isolators.
- ceramics are strong.
- they are very sensitive to notches (small cracks will initiate fracture).
- they are chemically stable.
- some ceramics are used as soft or hard magnetic materials.
PLASTICS
Use of Plastics
Compared with metals and ceramics, polymers (plastics) have the following characteristics:
- they deflect or deform much more than metals or ceramics.
- at room temperature, many plastics “creep” or slowly deform with time, which can lead to
deformation or fracture.
- Thermoset plastics are less strong than metals.

Thermoplastic – can be re-melted and re-cycled

Thermosetting – cannot be re-melted and re-cycled
 COMPOSITES
Composites are a three-dimensional combination of two or more materials, where each material can
be visually distinguished from the other.
Characteristics of composites are:
- they are corrosion resistant, less expensive and used in everyday application
- composites are stronger than unreinforced matrices and exhibit a higher resistance to fatigue

THE ATOM
The smallest functional portion of a chemical element is called the Atom. The atom consists of a nucleus, made up
of positively charged protons and uncharged neutrons, surrounded by electrons. In an electrically neutral atom, the
number of electrons will equal the number of protons cancelling the electrical charge of each.
It contains:
- Nucleus consisting of positively charged Protons and uncharged Neutrons, surrounded by negatively
charged electrons.
- Each electron shell (orbit) can contain only a definite number of electrons. The number of shells is determined
by the atomic number of the element.
Atomic Structure:
The arrangement of the parts of an atom, which consists of a massive positively charged nucleus surrounded by a
cloud of electrons arranged in orbits describable in terms of quantum mechanics. A molecule is the smallest part
of the compound ( a substance consisting of more than one kind of atom) that retains properties of that compound.

Atom – The individual structure which constitutes the basic unit of any chemical element.

Atomic Number – The number of protons in an atomic nucleus.

Atomic Weight – The relative mass of an atom based on a scale in which a specific
carbon atom (carbon-12) is assigned a mass value of 12.

Atomic Mass – The mass of a neutral atom usually expressed in atomic mass units.

Atomic Particle – electron, neutron, proton, the quantity of each constitute a specific atom.
Periodic Table
The properties of a metal are determined by the number of electrons in the ATOM.

Atomic Bonding

Three methods of atomic bonding are:

- Ionic Bonding – this type of bond occurs between a metal and a non-metal atom.
(salt)

- Covalent Bonding – can involve the sharing of more than one electron and occurs
between two non-metal atoms.

- Metallic Bonding – found in metals and their alloys. They are free to drift
throughout the entire material.
Solid State Changes in Metals:
Nearly all metals processed by MECHANICAL AND THERMAL methods are treated in the solid state
to obtain improved mechanical properties. There are two basic types of solids: crystalline and
amorphous. Crystalline being more commonly used.

Plastic State Shape Changes:

Reshaping the material in the plastic state is carried out in one of the following:
- Molding
- forging
- press-working
- rolling, or extrusion

 
 Solidification Phase of Metals:
Because cooling cannot be exactly the same for every atom, certain atoms will cool first and become the nucleus
for crystal formation. Imperfections in the crystal structure of metals are linear defects.
As the energy of a liquid metal is reduced by taking away heat (THERMAL ENERGY), the attraction between
atoms increases until they arrange themselves in definite 3-Dimensional geometric patterns that are called space
lattices.

Space Lattice:
A space lattice is a structure consisting of groupings of identical unit cells aligned in parallel planes. A single
cell does not exist alone. There are 14 types of crystal lattice structures. The most commercially important
metals in solid state (copper, steel, aluminum ) exist in one of 3 types of crystal lattice structures:
Body-centered cubic lattice (BCC),
Face-centered cubic lattice (FCC)
Hexagonal close-packed lattice (HCP)
 Body Centered Cubic Structure:
This type of cell is made up of nine atoms. Eight atoms are located on the corners of the cube and the ninth
atom positioned centrally between them.
- strong structure
- adopted by hard & strong metals

COMMON MATERIALS :

Ferritic stainless steel

Chromium

Molybdenum

Tungsten
 Face Centered Cubic Structure:
Face centered cubic grain structure are normally found in metals with good strength and moderate ductility.
In this case the unit cell consists of 8 atoms in each corner, 6 are centred in the cube faces,(one on each face),
for a total of 14.
Typical Materials are:
Gamma Iron (Austenitic)
stainless steels
Aluminum
Copper
Gold
Lead
Hexagonal Close-Packed Cubic Structure:
Made up of seventeen atoms.
Seven located on each hexagonal face with one on each corner and the seventh in the center. The
three remaining atoms take up a triangular position in the center of cell.
Calcium,
Cobalt,
Zinc,
Titanium,
Magnesium.
Metals with this structure are susceptible to work hardening.
 Slip, Twinning and Rotational Deformation:
Different structures deform differently under applied loads. Most materials experience some elastic deformation
before they plastically deform. Plastic deformation is the irreversible shear displacement of a crystal relative to
another crystal.
Permanent deformation of metallic crystals occurs in 3 ways: slip, twinning, and rotational deformation.
1. Slip deformation occurs by translation or sliding between the atomic planes within grain.
2. Twinning deformation occurs most easily under loads applies suddenly, rather than gradually. The grains deform by
twisting or reorienting a band of adjacent lattice forms.
3. Rotational deformation is when stresses below the elastic limit cause the crystals to be temporarily bent and deformed.
 

Figure 1.5 (a) Permanent deformation of a single crystal under a tensile Rotational deformation:
load. Note that the slip planes tend to align themselves in the direction
of the pulling force. This behaviour can be simulated using a deck of
cards with a rubber band around them. (b) Twinning in a single crystal
in tension.
 Approximate Equilibrium Heat-Treatment Process:
The Equilibrium Phase diagram illustrates the relationship between temperature, composition, and the phases
present in the particular alloy system.
Iron-Carbon Diagram:
Pure metal melts at a temperature of 1538° C (2800°F).
As it cools, it takes on a BCC structure forming the Pure-iron phase. At 1394°C (2541°F),
The structure changes to a FCC structure forming the gamma–iron phase- (Austenite).
Upon further cooling, it changes to a BCC structure again, where it is known to have the alpha–iron phase
(Ferrite).
This ability of a solid material to exist in multiple forms is know as Polymorphism.
 Allotropic Temperature Changes:
A few metals will change lattice structure upon heating & cooling to exist in different phases through various
temperature ranges. Such metals are said to be allotropic (can exist in more than one crystalline structure).
The Critical Temperature is the temperature at which a change in crystal structure phase or physical
properties occurs.

Iron is an allotropic material that changes upon heating to 912° C, changing from a BBC to FCC structure.

912 C is the CRITICAL TEMPERATURE for Iron (the TRANSFORMATION TEMPERATURE).

A Phase change is one from a liquid to a solid. Allotropic changes are similar to phase changes except it is a
structure change.

Iron in the temperature range up to 912° C is called alpha iron; from 912° C to 1,349° C, is called gamma
iron;
  and above the melting point of delta iron, 1,538° C, its delta iron.

The most effective change is the difference of carbon solubility in the two phases, which serves as the
basis for all heat-treat hardening and most grain-size control for steel.
Heat Treatment:
 Heat Treatment:
Heat treatment is often defined as intentional heating and cooling for control of properties.

It is performed to decrease hardness, increase ductility and to refine grain structure.

  Hardenability is the ability of the material to be hardened by forming martensite. 

Hardenability depends on the carbon content, grain size, cooling rate and the alloying elements present.

The cooling rate depends on the cooling medium.  Cooling is fastest using water, then oil, and then air. 

Quenching is a type of metal heat treatment process and involves the rapid cooling of a metal to adjust the mechanical
properties of its original state.  Quenching brings the danger of warping and formation of cracks, since it is usually
accompanied by large thermal gradients. 

The shape and size of the piece, together with the heat capacity and heat conductivity are important in determining the
cooling rate for different parts of the metal piece. 
 Heat Treatment of Steel:

Heat treatment processes that place the metal in either a complete or approximate equilibrium condition are:
- Austenizing
- Annealing
- Normalizing
- Spheroidizing

**Cracking caused by heat treatment can be found in areas of sudden change in thickness. High temperature gradients
contribute to high stresses that cause distortion and cracking.**

Change of properties of steel can be accomplished by cold working, by precipitation hardening, and by allotropic
changes.
  Austenitization:
 
In this phase, as much as 2% carbon can dissolve at the eutectic temperature of 1,148° C at which the widest
range of gamma composition exists. Grain sizes are affected only by increasing the temperature through this
range and not by decreasing temperature.

Grain Control During Austenization:

One of the important features of Austenization is grain refinement that occurs with the formation of the new
FCC lattice structure. These grains will remain small if the temperature is not raised too high or maintained too
long. Lowering temperature transforms the small grain austenite to BCC, with very little change to the grain size.

 Eutectic – a mixture of two or more substances having a similar melting temperature and the mixture behaves
like a pure compound. During the transformation from a liquid to a solid state there is a simultaneous
crystallization of the components involved.

Austenite – a solid solution of carbon in gamma iron.

 Annealing:
Annealing is a treatment consisting of heating to and holding at a suitable temperature (above the critical
temperature) followed by cooling slowly at a certain rate.
Annealing is used for softening and regaining ductility of a metal (sometimes in conjunction with cold
working )
During annealing process, new equiaxed and stress free grains replace the older grains in the
recrystallization phase. (This temperature may be higher than the material’s recrystallization temperature
depending on the degree of cold work.)
The purpose of annealing:
1. Decrease hardness
2. Increase ductility
3. Improve machinability
4. Relieve stress
5. Refine grain structure
6. Promote a uniform structure throughout
Types of Annealing are:
Process Anneal: also called intermediate annealing, is used to remove strain hardening due to previous cold
 Normalizing:
Normalizing is the heating of a ferrous alloy to a suitable temp. slightly above the full annealing
transformation range and then slowly cooled in still air to:
refine the grain structure
obtain uniform structure
reduce residual stresses.
Normalizing is similar to annealing except the steel is not reduced to its softest condition and the Pearlite is left
fine instead of coarse. An attempt is made to dissolve all the Cementite to eliminate the settling of hard, brittle,
iron carbide in the grain boundaries. Pearlite is a crystalline structure with layers of soft, ductile ferrite, and
hard, brittle cementite. Refinement of grain size, relief of internal stresses, and improvement of structural
uniformity together with recovery of some ductility provide high toughness qualities in normalized steel. The
desired decomposition products are small grained fine Pearlite with a minimum of free ferrite and free
Cementite.
Spheroidizing:
Minimum hardness and maximum ductility of steel can be produced by a process called Spheroidizing, which
causes the iron carbide to form in small spheres or nodules in a ferrite matrix. Spheroidizing produces the
minimum hardness and maximum ductility of steel. The main need for the process is to improve
machinability. Spheroidizing is not performed nearly as much as annealing or normalizing.
 Hardening of Steel:
Austenization is the first step. Most of the heat treatment hardening processes, for steel are based on the
production of high percentages of Martensite. The second step involves cooling rapidly in an attempt to avoid
pearlite transformation. High temperature gradients contribute to high stresses that cause distortion and cracking,
so the quench should be only extreme as is necessary to produce the desired structure. Cracks created by either
heating or quenching can be detected by various NDT surface examinations.
 
Hardening of steel is a four-step process: austenization, fast cooling, martempering and austempering

Tempering
A third step usually required to condition a hardened steel to a temperature below the transformation temperature
range for service is tempering, or as it is sometimes referred to, drawing. With the exception of austempered
steel, which is frequently used in the as-hardened condition, most steels are not serviceable “as quenched”.
Therefore the quench should only be as extreme as necessary to produce the desired structure. Heat must be
removed uniformly to minimize thermal stress.

Types of tempering are: 1. Martempering: quenching process to produce martensite.

2. Austempering: quenching process to produce bainite.
 Age Hardening:
Age hardening, precipitation hardening, and solution hardening, are all considered treatments separate
from solidification. It is used when there is a need to develop hardness or strength, or both. There are two
kinds of age hardening natural and artificial.
Precipitation Hardening - hardening caused by precipitation of a constituent from a supersaturated solid
solution.
Solution Hardening - heating of a alloy to a suitable temperature, and holding that temperature until one or
more constituents forms a solid solution.
The terms "precipitation hardening" and "solution heat treatment" are often used interchangeably when heat
treating nonferrous alloys

Work Hardening:
The effects of work hardening or deformation can cause two types of deformation.
Elastic If the load does not stress the material past its elastic limit, the deformation is “ elastic,” and the material
returns to its original position upon removal of the load.
Plastic When a material is stressed past it’s elastic limit. Plastic deformation occurs in one of three ways: slip,
twinning, and rotational deformation.
***The strength of the metal is increased by plastic flow beyond the elastic limit. ***
**A material that cannot be work hardened is one that recrystallizes at room temperature. i.e.. Lead , zinc, tin**
Other names for work hardening include cold working or strain hardening.
Case hardening or Surface hardening is done to harden the surface of a part(not the internal structure)
 Corrosion:
Corrosion is an undesirable process and may be defined as the degradation of material due to a reaction with
its environment .

The reaction may be the chemical action of some surrounding or contracting medium which may be liquid, gas,
or some combination of the two.

The special characteristic of most corrosion processes is that the oxidation and reduction steps occur at separate
locations on the metal.
 

 
 Types of corrosion :
 
general corrosion stress-corrosion cracking intergranular corrosion
galvanic corrosion filiform corrosion knife-line corrosion
corrosion pitting erosion crevice corrosion
GENERAL CORROSION
 This is characterized by a relatively uniform corrosion over the surface, it may occur throughout the vessel,
tank or pipe system.
 
GALVANIC CORROSION
 This type of corrosion is caused by the current of a galvanic cell made up of dissimilar metals such as iron &
copper, brass & aluminum.
This type of corrosion may occur where dissimilar metals are joined by welding or brazing, riveting or
mechanical forming. It can also occur on surfaces that are plated, sprayed or have other metal coatings or paints
applied.

PITTING CORROSION
Pitting corrosion is also known as concentration-cell corrosion which is the result of electrochemical potential
set up by a difference in the oxygen concentration between the inside and the outside of the corrosion pit.
Pitting corrosion is most likely to occur when there is no flow or a stagnant condition exists in the system.
Pitting corrosion is further enhanced by scratches, surface defects, or breaks in the protective layers.
 STRESS-CORROSION CRACKING:
 This is a combination of corrosion and tensile stresses, the tensile stresses are of a static nature. When cyclic
stresses are involved the cracking is called corrosion fatigue. There are specific environments for each alloy
where stress-corrosion cracking becomes more susceptible. An example of this is carbon steel, it will undergo
stress-corrosion cracking in hot nitrates, hot carbonate water and sulfo-nitric acids. Another example is austenitic
stainless steels in hot chlorides or copper alloys in ammonia. In the instance of cracking adjacent to welds, a
transverse crack is primarily the result of longitudinal weld shrinkage. A longitudinal crack in the heat affected
zone is caused by transverse shrinkage. The cracking right beside the weld bead is usually caused by undercut.
The longitudinal cracking in the center of the weld bead is usually caused by lack of penetration in the weld root
pass.

Filiform Corrosion:
A special form of crevice corrosion in which the aggressive chemistry build-up occurs under a protective film
that has been breached. This type of corrosion occurs under painted or plated surfaces when moisture
permeates the coating. Lacquers and "quick-dry" paints are most susceptible to the problem. The crawling under
paint corrosion called 'filiform'.
 EROSION:
 This type of corrosion is caused by the destruction of a metal by the abrasive action of a liquid or vapor. Solid
particles suspended in a liquid may further accelerate this type of corrosion. Erosion usually takes place in areas
where the flow is restricted or the direction of flow is changed. It may also occur around inlet or outlet nozzles,
at vessel or pipe walls opposite inlet nozzles, impingement baffles, in elbows or in valves where flow is reduced
or changed. When erosion is the result of the formation and subsequent collapse of cavities in a liquid, this
type of corrosion is known as cavitation.
 
INTERGRANULAR CORROSION:
 This type of corrosion is usually associated with stainless steels e.g. 304, 309, 310, 316 or 317. These materials
have been heated to or held at temperatures between 500 and 800 C and that have also been exposed to
corrosive environments. Corrosion then occurs quite rapidly along the grain boundaries. The sensitivity to
intergranular corrosion is caused by the formation of chromium carbide that depletes the chromium content
along the grain boundaries. Because of this change in the chromium content along the grain boundaries, steel is
also called sensitized.
 
KNIFE-LINE CORROSION:
 Knife-line corrosion occurs along the plane between base metal and weld metal. This type of corrosion is
usually found in austenitic stainless steels particularly those that contain molybdenum. This corrosion is usually
associated with the formation of carbides at temperatures near the melting point which promote localized
galvanic corrosion.
 CREVICE CORROSION:
 Crevice corrosion is sometimes referred to as contact corrosion as it often occurs at the location of contact
between nonmetallic materials and passive metals. When the protective materials present on the surface of
materials is broken or ruptured the corrosion starts. Crevice corrosion also represents concentration cell
corrosion. Crevice corrosion is quite common in threaded joints and may be prevented by the use of joint
compounds or brazing or soldering to prevent the seepage of liquids into the crevice.

Fretting - is corrosion-assisted wear resulting from small oscillatory movements between mating surfaces under
load.

Environmentally induced corrosion – is the result of the presence of a corrosive or chemically reacted
environment.

Some variations of corrosion are known by the names of season cracking, stress corrosion, and fretting, all of
which are corrosion systems in which corrosion is accelerated by the metal being under load at the same time
corrosion is occurring.

Corrosion Protection:
The general combat methods include: selection of the most suitable metals, treatment of or controlling the
 Recrystallization:
Recrystallization when used as in-process treatment can improve ductility, refine grains and relieve
stress.
This takes place after heating a cold worked metal. This is also referred to as process annealing.
The recrystallization temperature will vary from metal to metal. A term usually associated with this work
is recovery.

Recovery is the removal of work hardening effects and the formation of new strain free grains. It is
sometimes referred to as stress relief, involves rearrangement of some of the more strenuous dislocations
or imperfections with little or no effect on the external firm of the crystals or grains.

For most, it is necessary to heat treat a material to a specific temperature that will depend upon the degree
of recovery desired.
If the temperature is raised too high or maintained for too long a time, hardness and strength of the metal
will decrease appreciably, but high temperature treatment is sometimes necessary to remove residual
stresses in forgings and steel weldments. Although some of the major distortions are eliminated by
treatment for recovery, most of the distorted crystalline lattice remains as it was produced by cold work.

Recovery of ductility to permit further change of shape by deformation can be obtained only by
elimination of the deformed grains, and this can be accomplished by recrystallization.
Grain Boundary Dislocations:

Dislocations
It would be misleading to suppose that all the atoms in a piece of
metal are arranged in a regular way. Any piece of metal is made
up of a large number of "crystal grains", which are regions of
perfect regularity. At the grain boundaries atoms have become
misaligned and is here where interstitial defects may be
introduced.

Figure 10.5 Schematic illustration of three

basic types of cast structures: (a) columnar
dendritic; (b) equiaxed dendritic; and (c)
equiaxed nondendritic. Source: D. Apelian

Figure 10.6 Schematic illustration

of cast structures in (a) plane front,
single phase, and (b) plane front,
two phase. Source: D. Apelian.
 Crystal (Grain) Boundaries:
Grain Boundaries are interruptions in the orderly arrangement of the space lattice structure. These boundaries
offer resistance to the deformation of the metal. These areas of metal microstructure are where the grains
interfere and impinge on one another and where low melting impurities tend to concentrate.

Factors that can influence some methods of NDT are: grain size, orientation, and composition.
If two grains having the same orientation meet, they will join to form a larger grain. If they are forming
about a different axis, the last atoms to solidify between the growing grains will be attracted to each grain of
different orientation, and must assume a compromise position in an attempt to satisfy a desire to join both
grains.
These misplaced atoms form in layers around the grains and are known as “grain boundaries”.
A fine-grained metal with large numbers of interruptions, therefore, will be harder and stronger than
a coarse-grained metal of the same compositions and condition.
This is where low melting impurities are. (Gamma iron).
Grain size, grain orientation, and the composition of grain boundaries are factors that can influence
some NDT test.
Importance of Crystal (Grain) Size
Grain size has an important influence on the mechanical properties of a metal and
fortunately, can be controlled by methods much more precise than manipulation
of the factors that influence growth during solidification.

Coarse grained materials: have lower strength than fine grained materials.
Machine more easily, require less energy for processing, easier to harden by heat
treatment, although the quality of surface produced will not be as good as with a
fine-grained material Increased susceptibility to cracking under thermal loads and
will case-harden more easily. Coarse grains may sometimes be necessary in the
final product to provide the best mechanical properties. Some deformation
processes of shaping materials can be used so as to cause grain-size reduction
automatically during the shaping process with little or no additional cost
involved.
Fine grained materials: with large numbers of interruptions or grain boundaries, are harder and
stronger than a course grained metal of the same composition and condition. Fine grains are usually
necessary in the final product to provide the best mechanical properties. Some deformation processes
of shaping materials can be used to refine grain structure automatically during the shaping process with
little or no additional cost involved.
 Grain Structure:
This pine tree-like shaped solidification is known as dendritic growth.

Grain size will dictate the mechanical properties of a metal;

1. Hardness
2. Ductility
3. Strength
A coarse grained metal will;
1. Less strength
2. Machine more easily
3. Have a reduced surface quality.
The grain structure of many metals can be controlled by heating and cooling.

The control of solidification is one of the controlling factors in determining the grain size of a metal
.
Grain size will dictate the mechanical properties of a metal; Hardness, Ductility, Strength.
 Grain :

Figure A, we may have ferrite grains in a non- heat treated or non-hardenable body-centered cubic (bcc) metal
or alloy
Figure B depicts a single phase austenitic alloy that contains annealing twins

Figure C shows the twinned austenitic grain structure of cartridge brass that was etched producing grains with
different contrast in black and white

Figure D, shows AlSl 316L stainless steel electrolytically etched with 60% nitric acid in water (Pt cathode, 0.8
V dc, 45 s). The grain boundaries are almost completely revealed but no twins are visible.
Figure E, shows a tint etched view of this specimen at the same magnification where the twins are visible.

Figure F, is not very good if actual measurements are made, especially if image analysis is employed. The
alternative is to darken the grain boundary cementite films. A number of etchants will darken cementite, the
one used here,

Figure G, was Beraha's sodium molybdate tint etch but the familiar alkaline sodium picrate etch works well
also. Etched in this way, the grain structure shows up much more clearly and image analysis could be used.

Figure H illustrates a fairly successful effort with a quenched and tempered experimental alloy steel.