Lecture 3

Essential materials science (ctd)

1. Metals
I. Miller indices in cubic systems
II. Alloys and phase diagrams.
2. Ionic ceramics.
3. Covalent crystals
I. Silicon
II. Carbon-based materials
 Point coordinates in crystal
cubic structures
z Point coordinates for unit cell center
111 are
c (a/2,b/2,c/2) (½,½,½)

T
y Point coordinates for unit cell corner
a 000 h
e
b are (1,1,1)
p
i
x c
t
u
r
e
Translation: integer multiple of lattice
c
a
constants à identical position in
n
’
another unit cell
t
b
e
d
2
i
s
 Crystallographic directions
z Algorithm
1. Vector repositioned (if necessary) to start at
origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to integer values
4. Enclose in square brackets, no commas
x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a negative
index
Families of directions <uvw>

3
 Crystallographic planes
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions & common
multiples. All parallel planes have same Miller indices.

• Algorithm
1. Read off intercepts of plane with axes in terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to integer values
4. Enclose in parentheses, no commas, i.e., (hkl)

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 Crystallographic planes

example a b c c
1. Intercepts 1 1 ¥
2. Reciprocals 1/1 1/1 1/¥
1 1 0
y
3. Reduction 1 1 0
a b
4. Miller Indices (110)
x

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 Crystallographic planes

z
example a b c
1. Intercepts 1/2 ¥ ¥ c
2. Reciprocals 1/½ 1/¥ 1/¥
2 0 0
3. Reduction 2 0 0 y
4. Miller Indices (200) a b

Family of planes {hkl}, e.g. {100}

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Crystallographic planes

7
 Alloys
and
phase diagrams

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The iron-carbon “phase diagram”

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The iron-carbon “phase diagram”

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 Teminology
Metallic alloy – mixture of a metal with other metals or non-metals;
ceramics too can be mixed to form ceramic alloys

Components – the chemical elements that make up alloys

Binary alloy – alloy containing two components;

ternary alloy contains three, quaternary alloy four, and so on

Concentration – defines the amount of components in weight or atomic %

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 Teminology
Phase – all parts of an alloy microstructure with the same atomic
structure are a single phase

In a binary alloy the solid microstructure takes one of three

forms:
• A single solid solution
• Two separated solid solutions
• A chemical compound, with a separated solid solution

Solid solution – a solid in which one or more elements are

dissolved in another so that they are homogenously dispersed at
an atomic scale

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 Teminology
Constitution of an alloy:
• Phases present
• Weight fraction of each phase
• Composition of each phase

Thermodynamic equilibrium – the constitution is stable and

there is no further tendency for it to change

Equilibrium constitution – state of lowest Gibbs free energy G,

for a given composition, temperature, and pressure

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 Single Component Phase Diagrams
Water

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 Simple Phase Diagrams

Phase diagram – diagram with temperature and composition as axes,

showing the equilibrium constitution.

Liquidus line – phase boundary that limits the bottom of the liquid field.

Solidus line – phase boundary giving the upper limit of the single-phase
solid field. 15
 Simple Phase Diagrams
Isomorphous phase diagram – simplest possible example where the solid-
state is a solid solution for all compositions; this behavior is unusual because
there is almost always a limit to how much one element can be dissolved in
another

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 Triphasic equilibria in binary phase
diagrams: eutectic type
Eutectic reaction L cooling
a+b L
heating a b
a+b

Eutectoid reaction a cooling

b+g aa
heating b g
b+g

Monotectic reaction L1 cooling a + L2 L1

heating a L2
a+L2

17 17
Simple Phase Diagrams

Completed phase diagram showing the

solubility limits for the single phases, and the
eutectic point closing the liquid field – the
single-phase fields are shown separated by
the two-phase fields.

Eutectic point – lower limit of the

single-phase liquid field formed by the
intersection of two liquidus lines.

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 Triphasic equilibria in binary
phase diagrams: peritectic type
cooling
Peritectic reaction L+ a heating
b
a
L+a
L

Peritectoid reaction a+b cooling

g a +b b
heating a
g

Synthetic reaction L1+ L2cooling b L1+L2 L2

L1
heating
b

19 19
Simple Phase Diagrams
Peritectic point – inverted ‘V’ at
which the austenite field closes; max
temperature at which this single
phase forms

Eutectoid point – lower limit of a

single-phase solid field formed by
two falling phase boundaries
intersecting in a ‘V’
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Solidification of Dilute Alloys

21
Segregation

Out of equilibrium solidification

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 Metals case study:
shape memory alloys

A stent is a mesh tubular structure

often used in conjunction with
angioplasty to permanently hold
open an artery, allowing for
unrestricted blood flow, or to
support a weaked artery wall
(aneurysm).

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 Metals case study:
shape memory alloys
Shape Memory Alloys (SMAs) are a class of metal alloys that can
recover apparently permanent strains when they are heated
above a certain temperature. They do so through reversible
martensitic transformations.

Remarkable devices that exploit the shape memory effect (a

consequence of certain martensitic transformations) such as stents
that open up once at body temperature.

The terms austenite (parent, high temperature phase) and

martensite (product phase or low temperature phase, that
appears without a change in composition) are borrowed from
steels.
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 Metals case study:
shape memory alloys
1932: Discovery of reversible martensite to austenite phase
transformation in Au-Cd alloying system by Chang & Read

1951: Discovery of recovery of deformed shape in Cu based alloys

by Genevray

1962: Discovery of shape memory Effect in Ni-Ti alloying system by

William G. Buhler in Naval Ordnance Laboratory

1970: First Commercial Use of Nitinol in F14 Tomcat

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 Metals case study:
shape memory alloys
A shape memory alloy (SMA) "remembers" its original shape and after being
deformed returns to that original shape by heat application. This type of material
can replace conventional actuators such as hydraulic, pneumatic and motor-based
systems. Shape memory alloys have applications in industries including medical
and aerospace.
The high-temperature austenitic
structure undergoes twinning as
the temperature is lowered. This
twinned structure is called
martensite. The martensitic
structure is easily deformed into a
particular shape through stress
application (twins re-orientation or
detwinning). When heated, the
deformed martensite resumes its
austenitic form, resulting in a
macroscopic shape memory
phenomenon.
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 Metals case study:
shape memory alloys

Deformed martensite (at Heating induces

room temperature) transformation to
austenitic original
form

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 Metals case study:
shape memory alloys
• In spite of the SMA variety, only Ni-Ti (Nitinol) and Cu-based
alloys are commercialized.

• Ni-Ti leads the market:

– Higher memory capacity (deform ∼8% against ∼ 4% of Cu-
based alloys)
– Higher thermal stability
– Higher corrosion resistance
– Large range of transformation temperatures

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Ionic ceramic structures

29
 Ceramic crystal structures

• Bonding:
- Mostly ionic, some covalent.
- % ionic character increases with difference in electronegativity.

• Large vs small ionic bond character:

CaF2: large

SiC: small

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 Ionic ceramic structures:
site selection
Cations are smaller than anions and occupy the interstices of the
anions’ substructure. Which sites will cations occupy?

1. Size of sites
– does the cation fit in the site?

2. Stoichiometry

3. Bond hybridization
– hybrid orbitals can have impact if significant covalent
bond character is present

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 Site selection
i) Size
• Stable structures
- Maximize the number of nearest oppositely charged neighbors.

- - - - - -
+ + +
- - - - - -
unstable stable stable

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 Site selection

ii) Stoichiometry
• Charge neutrality: the net charge in the structure must be zero.

A mXp F-
CaF 2 : Ca 2+ +
cation anions
m, p determined
by charge neutrality F-

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 Ionic ceramics structures
r cation
• Coordination number increases with
r anion
Question: How many anions can you arrange around a cation?
rcation
ranion Coord #

< 0.155 2 linear ZnS

(zinc blende)
0.155 - 0.225 3 triangular

0.225 - 0.414 4 tetrahedral (TD) NaCl

(sodium chloride)
0.414 - 0.732 6 octahedral (OH)

0.732 - 1.0 8 cubic CsCl

(cesium chloride)

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Common ionic ceramic
structure types

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 Sodium and sodium chloride
Na NaCl

BCC structure

EF

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Covalent

crystals

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Covalent bond:
i) covalent crystals: silicon and
carbon allotropes
ii) polymers (later…)

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Carbon allotropes

39
Diamond: C (sp3)

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 Diamond: C (sp3)

8x(1/8)+6x(1/2)+4 =
= 8 atoms/unit cell

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Diamond: C (sp3)

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 Carbon: C (sp3)
n C atoms
4n sp3 levels
3n 2p levels
2p levels

n 2s levels
2s levels

Internuclear distance
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 Graphite: C (sp2)
Diamond: C (sp3) p Delocalization

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Graphite: C (sp2)

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Graphite: C (sp2)

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Graphene: C (sp2)

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Graphene: C (sp2)

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 Carbon nanotubes (CNT)

49 49
 Carbon nanotubes (CNT)
(n,n) (n,0) (n,m)

SWNT = Single wall nanotube

CNT is a tubular form of carbon with

diameter as small as 1 nm. Length: few
nm to microns.

CNT is configurationally equivalent to a

single or multiple two dimensional
graphene sheet(s) rolled into a tube
(single wall vs. multiwalled).

Models of different single wall nanotubes

50 50
 Carbon nanotubes (CNT)
Chirality of a stripe of graphene rolled into a tube

(n,m)

51 51
 Carbon nanotubes (CNT)

zigzag

armchair

52 http://www.tyndall.ie/research/electronic-theory-group/nanotube.html 52
 CNT properties
• The strongest and most flexible molecular material because
of C-C covalent bonding and hexagonal network architecture.

• Young’s modulus (~diamond) >1 TPa vs 700 GPa for C-

fiber vs 200 GPa for steel and 70 GPa for Al.

• Tensile strength ~200 GPa. Strength to weight ratio 500x

that of Al; similar to steel and titanium; one order of
magnitude improvement over graphite/epoxy composites.

• Maximum strain 10%; much higher than any metal or

ceramic

• Multiple tubes slide inside of each other with minimal

effects of friction.

• Thermal conductivity ~ 3000 W/mK in the axial direction

with small values in the radial direction.

53 http://www.ipt.arc.nasa.gov/gallery.html
 CNT properties
• Can be metallic or semiconducting depending on chirality:
!"#
- metallic if is an integer and semiconductor if not
$
-‘tunable’ energy gap
- electronic properties can be tailored through application
of external magnetic field, application of mechanical
deformation…

• Electrical conductivity higher than copper.

• Very high current carrying capacity (107 - 109 A/cm2) 1000x

that of Ag or Cu.

• Various chemical groups can be attached to the tip or

sidewall (‘functionalization’)
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 CNT applications

Synthesis of CNT–peptide conjugates

Adv. Mater. 26, 1846–1885 (2014) 55

 Fullerenes

Hollow
C60
•
• Spherical fullerenes are called ‘Buckyballs’
• Can be used as lubricants.
• Applications in electronics and optoelectronics
• Lower melting point than graphite or diamond

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 Electrical Special
conductivity property
Poor Hardest substance
No free electrons Good thermal conductivity
(insulator) Jewelry
Diamond
Good Soft material
Higher within the layers Layer slide across each other
(p delocalization) Lubricant
Graphite Filler in composites
Very good Lightest/strongest material
Within the layer Transparent electrode for electronics
(p delocalization) Filler in composites
Graphene Drug delivery

Good Organic electronics

Chirality dependent Cancer therapy and cancer imaging
(metals/semiconductors) Filler in composites
Carbon nanotubes
Semiconductor Photovoltaic cells and transistors
Packing dependent Drug delivery
(p delocalization) Target cancer cells
Filler in composites
Fullerenes
Silicon: Si (sp3)

Isostructural with diamond

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Silicon: Si (sp3)

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Semiconductors

60
 Band structure of crystalline
materials and electrical properties
Conductor Semiconductor Insulator

61
Carbon fiber
Polyacrylonitrile

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Carbon fiber

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64
Heating at 600 to 1300 oC

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