CRYSTAL STRUCTURES

DEFECTS in CRYSTALS
Movement of Dislocations
• Close-packed planes are known as slip or glide planes. A slip system describes the set of symmetrically
identical slip planes and associated family of slip directions for which dislocation motion can easily occur
and lead to plastic deformation.

Slip in face centered cubic (fcc) crystals occurs along the

close packed plane. Specifically, the slip plane is of type
{111}, and the direction is of type <110>. fcc crystals have
12 slip systems.

There are no truly close-packed planes in the bcc crystal

structure. Thus, a slip system in bcc requires heat to activate.
Some bcc materials (e.g. α-Fe) can contain up to 48 slip systems.

Slip in hexagonal close packed (hcp) metals is much more limited

than in bcc and fcc crystal structures. Usually, hcp crystal structures
allow slip on the densely packed basal {0001} planes along the
<1120> directions.
 CRYSTAL STRUCTURES
DEFECTS in CRYSTALS
Images of Dislocations

Dark Field Bright Field

 CRYSTAL STRUCTURES
DEFECTS in CRYSTALS
Images of Dislocations
 CRYSTAL STRUCTURES
PROPERTIES DEPENDING ON DISLOCATION MOTION

Strain Hardening
 Yield Strength
 Ductility
 Tensile Strength
Strain Hardening
Strain hardening is one of the most commonly used
means of adding strength to an alloy. It is simply the use
of permanent deformation to increase the strength of the
metal. Other names for strain hardening are cold work
and work hardening

Dislocations interact with each other

and can assume configurations that
restrict the movement of other
dislocations.
The situation gets more severe as the
dislocation density increases leading to
an increase in the flow stress.
Strain Hardening
To properly discuss strain hardening,
let’s first consider the plastic
deformation of a single crystal. Plastic
deformation is initiated at a critical
stress, the critical resolved shear stress
(CRSS).

τCRSS = σyscosφ cosλ

Schmid's Law states that the critically resolved shear stress is equal to the stress applied to the
material multiplied by the cosine of the angle with the vector normal to the glide plane and the
cosine of the angle with the glide direction.
Illustration of the slip mechanism on a tension test of a single crystal of cadmium.
 Non Crystalline Solids
Non- crystalline solids are “amorphous solids”. Unlike crystalline solids, they do not have a definite geometrical
shape. The atoms in solids pack closely together than in liquids and gases.

However, in non-crystalline solids, particles have a little freedom to move since they are not arranged rigidly as
in other solids. These solids form after sudden cooling of a liquid. The most common examples are plastic and
glass.
 Non Crystalline Solids
Difference between Crystalline and Non crystalline solids

• In crystalline solids, constituent particles (atoms, molecules or ions) arrange in a three-

dimensional periodic manner. Non-crystalline solids do not have a consistent arrangement of
particles. So, non-crystalline solids are amorphous solids.

• With regard to the geometry of these solids, crystalline solids have a well-defined geometrical
shape due to the regular arrangement of unit cells, unlike Non-crystalline solids that do not have
well–defined geometrical shape.

• crystalline solids have a symmetry while non-crystalline solids do not have symmetry at
localized point

• Furthermore, crystalline solids have a long range order while non-crystalline solids have a short
range order.

Crystalline solids have a high fixed value for the heat of fusion and a definite melting point.
However, non-crystalline solids do not have a fixed value for the heat of fusion and they melt over a
range.
 Non Crystalline Solids

Crystalline (Quartz)

Silica (SiO2)

Amorphous (Glass)

Amorphous (Glass) : configurationally frozen liquids

Difference between liquids and amorphous material  viscosity

Due to lack of crystal structure – dissolves easily  Potential application : medicine

 Non Crystalline Solids
Preparation of Amorphous Solids
Glass formation is a matter of bypassing crystallization. The channel to the crystalline state is evaded by quickly
crossing the temperature interval between Tf and Tg.
Nearly all materials can, if cooled quickly enough, be prepared as amorphous solids.

Melt Quenching
Also called splat quenching, can quench a droplet of a molten metal roughly 1,000 °C
in one millisecond, producing a thin film of metal that is an amorphous solid

Vapour condensation techniques

Amorphous solids can still be prepared by dispensing with the liquid phase
completely and constructing a thin solid film in atom-by-atom fashion from the gas
phase. A vapour stream, formed within a vacuum chamber by thermal evaporation of
a sample of the material to be deposited, impinges on the surface of a cold substrate.
The atoms condense on the cold surface and, under a range of conditions (usually a
high rate of deposition and a low substrate temperature), an amorphous solid is
formed as a thin film
 Non Crystalline Solids
Preparation of Amorphous Solids
Glass formation is a matter of bypassing crystallization. The channel to the crystalline state is evaded by quickly
crossing the temperature interval between Tf and Tg.
Nearly all materials can, if cooled quickly enough, be prepared as amorphous solids.

Other techniques

In melt spinning, a jet of molten metal is propelled against the moving surface of a
cold, rotating copper cylinder. A solid film of metallic glass is spun off as a
continuous ribbon at a speed that can exceed a kilometre per minute.

In laser glazing, a brief intense laser pulse melts a tiny spot, which is swiftly
quenched by the surrounding material into a glass.

In sol-gel synthesis, small molecules in a liquid solution chemically link up with each
other, forming a disordered network
 Non Crystalline Solids
Applications of amorphous solids
There are many applications of amorphous solids, some of them are:

• The glass is widely used in packaging (food jars, cosmetics box, and soft-drink
bottles), making tableware (utensils), in the construction of buildings ( windows,
lighting, and shelves) etc.

• Rubber is mainly used in manufacturing of tires, footwear, ropes, camp cloth and
as a raw material for several industries.

• Use of polymer can be seen in manufacturing of pipes, medicines and as a raw

ingredient for many factories.

• Amorphous silicon is considered as the best photovoltaic material to convert

sunlight into electricity
 Ores and Minerals
of common metals

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Earth’s layers
o Core
o ~Half of Earth’s radius
o ~16.1% of Earth’s volume
o Mantle
o ~82.5 % of Earth’s volume
o Crust
o Outermost layer
o ~1.4 % of Earth’s volume Source: 3.1 Earth’s Layers: Crust, Mantle,
and Core – Physical Geology, First University
of Saskatchewan Edition (usask.ca)
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o Oxygen – 46.1%
o Silicon – 28.2%

~ 88 %
o Aluminium – 8.23%
o Iron – 5.63 %
o Calcium – 4.15%
o Sodium – 2.36%

Source: Which elements make up most of the Earth's

crust? | World Economic Forum (weforum.org)
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Minerals and ores
o Metals
o Elemental form – useful
o Compounds
o Combined with other
elements
o Oxides, carbonates, sulfides
o Native metals
o Not combined with other
metals
o Au, Pt, Ag, Cu Source: 22.3: Metallurgy - Chemistry LibreTexts

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Minerals and ores
o Minerals
o Naturally occurring substances in Earth’s crust.
o Inorganic, regular crystal structure, solid at room temperature
o Enrichment - natural geological process
o Ores
o Naturally occurring mineral – extract one or more useful elements/compounds
o Valuable and economical to extract
o Gangue
o No economic value
Source: 3 Minerals – An Introduction
to Geology (opengeology.org)
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Important metals and their ores

Source:
https://img.brainkart.com/imagebk39/Zv8yiDU.jpg

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Department of Metallurgical Engineering
Native metals
o High value
o May require no
processing
o First metals
ever used

Source: 9 Ore Deposits and Economic Minerals – Mineralogy (opengeology.org)

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CLASSIFICATION OF EXTRACTIVE METALLURGY

Pyrometallurgy Hydrometallurgy Electrometallurgy

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CLASSIFICATION OF EXTRACTIVE METALLURGY

Pyrometallurgy Hydrometallurgy Electrometallurgy

• Uses Heat (High Temp)
• Basis – To make ore unstable by
taking to high temperature
• Use of reducing agent is
involved either solid (ex: coke,
coal) or liquid (reforming gas,
natural gas etc)
• Metal may be obtained in solid
or liquid form. Rarely in gaseous
form
• Flux is used in addition to
reducing agent. – to form slag of
lower MP or density.
• Criteria : when ore has
intermediate stability
• Ex: extraction of Fe, Zn, Sn, Pb,
Cu etc.
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Department of Metallurgical Engineering
CLASSIFICATION OF EXTRACTIVE METALLURGY

Pyrometallurgy Hydrometallurgy Electrometallurgy

• Uses Heat (High Temp) • Use of aqueous solution
• Basis – To make ore unstable by (acid+water+salts) or
taking to high temperature (alkali+water)
• Use of reducing agent is • Dissolution process where metal
involved either solid (ex: coke, gets selectively dissolved
coal) or liquid (reforming gas, whereas gangue material
natural gas etc) remains as solid residue.
• Metal may be obtained in solid (Thorium – reverse)
or liquid form. Rarely in gaseous • Based on chemical reactivity
form difference between metallic ore
• Flux is used in addition to and gangue.
reducing agent. – to form slag of • Criteria : if ore is low grade
lower MP or density. (lean) – lot of gangue compared
• Criteria : when ore has to ore. Or we want to recover
intermediate stability metals from secondary sources
• Ex: extraction of Fe, Zn, Sn, Pb, like slag, dross, e-waste etc.
Cu etc.
13-Feb-24 MT-101; IMME
• Ex: extraction of Cu, Ag, Au, Dr. Deepak K 114
Th,Department
U of Metallurgical Engineering
CLASSIFICATION OF EXTRACTIVE METALLURGY

Pyrometallurgy Hydrometallurgy Electrometallurgy

• Uses Heat (High Temp) • Use of aqueous solution • Use of Electricity (DC)
• Basis – To make ore unstable by (acid+water+salts) or • Sometimes both High Temp and
taking to high temperature (alkali+water) Electricity are used
• Use of reducing agent is • Dissolution process where metal • Metals of high purity (>99.9)
involved either solid (ex: coke, gets selectively dissolved can be obtained.
coal) or liquid (reforming gas, whereas gangue material • Contains electrolytic cell,
natural gas etc) remains as solid residue. electrodes, Electrolyte, DC
• Metal may be obtained in solid (Thorium – reverse) Current source.
or liquid form. Rarely in gaseous • Based on chemical reactivity • Criteria: When ore is highly
form difference between metallic ore stable
• Flux is used in addition to and gangue. • Electrolyte may be molten metal
reducing agent. – to form slag of • Criteria : if ore is low grade or aqueous.
lower MP or density. (lean) – lot of gangue compared
• Criteria : when ore has to ore. Or we want to recover
intermediate stability metals from secondary sources
• Ex: extraction of Fe, Zn, Sn, Pb, like slag, dross, e-waste etc.
Cu etc.
13-Feb-24 MT-101; IMME
• Ex: extraction of Cu, Ag, Au, Dr. Deepak K 115
Th,Department
U of Metallurgical Engineering
Extractive metallurgy
o Pyrometallurgy
o Processing at high temperatures > 1000oC
o Smelting, roasting, and refining
o High-grade ores – high percentage of the desired metal; lower impurities
o Higher yield, require lesser energy
o Expensive to mine
o Hematite (Fe2O3); Chromite (FeCr2O4); Cassiterite (SnO2), Galena (PbS)

01-Feb-24 MT-101; IMME Dr. Deepak K 116

Department of Metallurgical Engineering
Extractive metallurgy
o Hydrometallurgy
o Selective recovery of metals from low grade ores using aqueous solutions
o Leaching
o Ore + liquid solvent (acid or base or complex agent)
o Purification and recovery – precipitation, solvent extractions, electrowinning
o More electropositive metal displaces less electropositive metal from compounds
o Zinc in the solution of Copper Sulfate
o Effective for low-grade ores
o Electropositive elements – high reactive and pyrometallurgy is difficult

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Department of Metallurgical Engineering
Extractive metallurgy
o Electrometallurgy
o Electrical energy – electrolytic cells
o Electrowinning - extraction
o Electrorefining – purification
o Selective oxidation of impurities under electric current
o Expensive process

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Department of Metallurgical Engineering
Steps involved

Extraction of metals from ores

Concentration of ore Reduction Refining

o Removal of non-ore o Mineral contain several o Impurity in metal is directly

components economically desirable metals. related to the cost
o Separate out as much of o Break down of ore into o Refining is carried out to the
the waste mineral material valuable metals extent of desired properties

Magnetic Liquation
Pyrometallurgy
separation
Froth Electrolysis
Hydrometallurgy
flotation
Distillation
Density
Electrometallurgy
separation
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Department of Metallurgical Engineering
Pyrometallurgy processes

Pyrometallurgy

Roasting/Calcination Reduction (Smelting) Refinement

Processes depends on the composition of ore, concentrate and thermodynamic,

kinetic and environmental constraints

Noble metals – Commonly occurring in their metallic state – are removed from the ore
and refined.
Other metals – Occur as oxides or sulfides or carbonates – reduction needed before
refinement.

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Department of Metallurgical Engineering
Pyrometallurgy
o Oxide ores
o Carbothermically reduced by using coke, coal, or natural gas a reducing
agents
o Easier to reduce metal oxides than sulfides/carbonates
o Sulfide/carbonate ores
o Convert to oxide ores
o Roasting – sulfide ores
o Calcination – carbonate ores

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Department of Metallurgical Engineering
Roasting/Calcination
o Roasting 2ZnS+3O2 --> 2ZnO + CO2
o Heating of Sulphide ores below melting temperature under excess air
o Involves oxidation, reduction, sulfation, chlorination and pyro hydrolysis.
o Releases a large number of harmful gases into the environment.
o Calcination
o Heating of Carbonate ores below melting temperature in either absence or
limited supply of air.
o Involves thermal decomposition.
CaCO3 --> CaO + CO2
o Releases CO2.

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Department of Metallurgical Engineering
Smelting
o One of oldest and common smelting process involves
o Heating ores in the presence of Carbon, a reducing agent
o Source of carbon: Charcoal, Coal, Coke (crude form of carbon prepared by
pyrolysis)
o Basic reactions MO + C M + CO
M + ½ O2 M + ½CO2
MO + CO M + CO2
o Both M and C effectively compete for oxygen atoms
MO M + 1/2O2 ΔGo>0
C + 1/2O2 CO ΔGo<0
o Smelting process depends on the different ways in which the Gibbs energies of
reactions vary with temperature
https://chem.libretexts.org/Courses/University_of_Missouri/MU%3A__1330H_(Keller)/23%3A_Metals_and_Metallurgy/23.2%3A_Pyrometallurgy

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Department of Metallurgical Engineering
Smelting
o Temperature dependence is dominated by the change in entropy
ΔG° = ΔH° − TΔS°
o Entropy change (ΔS) - change in the number of moles of gas (Δng)
o Removal of oxygen from ore is accompanied by positive ΔS, reaction
becomes spontaneous at higher temperature

https://chem.libretexts.org/Courses/University_of_Missouri/MU%3A__1330H_(Keller)/23%3A_Metals_and_Metallurgy/23.2%3A_Pyrometallurgy

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Department of Metallurgical Engineering
Ellingham diagram
o Standard free energy of reaction as a
function of temperature
o Metal to oxides, one mole of Oxygen
o Slope
o Intercept

Welcome to Chem Zipper.com......: Ellingham

Diagram and it's features:
01-Feb-24 MT-101; IMME Dr. Deepak K 125
Department of Metallurgical Engineering
Ellingham diagram

MO M + 1/2O2

Below that of at least one of the oxygen-

consuming reactions

https://chem.libretexts.org/Courses/University_of_Missouri/MU%3A__1330H_(Keller)/23%3A_Metals_and_Metallurgy/23.2%3A_Pyrometallurgy

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 New and Advanced
Materials for Next
Generation

05-02-2024 127
Nanomaterial
Nanomaterials are usually considered to be materials with at least one
external dimension that measures 100 nanometres or less or with internal
structures measuring 100 nm or less. Ex: Carbon nanotubes (CNTs) ·
Nanocomposites · Nanofibers · Nanowires · Dendrimers · Quantum Dots
(QDs)

Biomaterial
A material derived from, or produced by, biological organisms like
plants, animals, bacteria, fungi and other life forms. Ex: hyaluronic
acid, chitin, cellulose, silk, chitosan, gelatin, and fibrin.
Biomaterials are commonly used in various medical devices and
systems: synthetic skin, drug delivery systems, tissue cultures,
hybrid organs, synthetic blood vessels, artificial hearts, cardiac
pacemakers, screws, plates, wires and pins for bone treatments,
total artificial joint implants
06-02-2024 128
Graphene and Carbon Nanotube
• Graphene is an atomic layer of carbon that is one atom thick. It has
incredible strength and is incredibly flexible and transparent. Graphene
is a million times thinner than human hair but 200 times stronger than
steel. It is also a better conductor than copper and is completely
flexible.
• Graphene has a lot of promise for additional applications: anti-corrosion
coatings and paints, efficient and precise sensors, faster and efficient
electronics.

• Carbon nanotubes (CNTs) are tubes made of carbon. CNTs are

cylindrical molecules tubes composed of carbon atoms (graphene).
• Nanotubes are 100 times stronger than steel. CNTs are good conductors
of heat and electricity depending on their configuration. Moreover,
CNTs are stiff like diamonds, elastic, have high thermal capacity, and
are one-sixth the density of steel.
• They have many potential applications in various areas such as
automobile, medicine, energy, aerospace, defense, structural and
chemical industries.
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Metal Foam
• Metal foam is solid metal with pore-like, gas-filled cells, or “porosity”
in the form of gas. Metal foams are highly porous and have a volume of
5 to 25% of their base metal and 75-95% of the material is empty, filled
with air.

• Their high porosity makes them ideal for use in a variety of

applications, including aerospace and mechanical components. There
are numerous benefits to foamed metal. It has the flexibility and
porosity to encase objects, such as bullets, in its dense material.

Metamaterials
• Metamaterials are materials that have both a crystalline and
an amorphous state.
• Metamaterials have incredible properties, like light-bending
abilities or superconductivity, that come from their
structure.
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Functional Materials
Functional materials are a group of engineered and advanced
materials designed and synthesized for some specific function. They
have one or more properties that can be significantly changed in a
controlled fashion by external stimuli

High Entropy Alloys

an alloy including five or more metal principal components with
equal atomic ratios. It exhibits the unique properties of high
hardness, high strength, excellent corrosion resistance, and
oxidation resistance.
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Auxetic Materials
Auxetic are materials that when stretched, thicken perpendicular to
the direction it is being stretched. In other words, instead of thinning,
they get fatter when stretched. Auxetics materials exhibit a negative
Poisson’s ratio.

Bulk Metallic Glasses

Bulk Metallic Glasses (BMG) are metallic alloys that have the
ability to solidify in an amorphous state.
These glass-forming metallic alloys vitrify at relatively low cooling
rates (from the molten state), compared with conventional rapidly
quenched metallic glasses.
They have unique properties such as superior mechanical strength,
high fracture toughness, high elastic strain limit, and lower Young’s
modulus.
They have great potential in biomedical applications ranging from
orthopedic, cardiovascular to dental implants and fillers
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 Quasi Crystalline Solids
Matter formed atomically in a manner somewhere between the amorphous solids of glasses (special forms of
metals and other minerals, as well as common glass) and the precise pattern of crystals.

Quasicrystal, is a structure that is ordered but

not periodic. A quasicrystalline pattern can Quasicrystal possesses rotational, but not
continuously fill all available space, but it lacks translational symmetry.
translational symmetry.
 Quasi Crystalline Solids

Artistic representation of dense packing of dodecahedra in space (source: Pinterest, Regolo Bizzi). Right) A Ho–Mg–Zn
quasicrystal in the shape of a dodecahedron
 Quasi Crystalline Solids
Quasicrystals are hard and brittle materials and their use is currently
limited to only a few niche applications.

Low-friction Al-Cu-Fe-Cr quasicrystals are used as a coating for frying

pans, while the addition of small quasicrystal particles can be used for the
hardening of steel.
Dan Shechtman, a scientist who despite all the
opposition and common wisdom dared to stand for the
idea of quasicrystals was in 2011 awarded with Nobel
Prize for Chemistry.

When asked to advise aspiring scientists, he said,

“Look for something that seems impossible, look for

something that cannot be”.