EEAC001

Materials Science and Engineering

Chapter 1: Introduction

Research in Computational Materials Group:

Generation of crystal defects and melting in a metal target irradiated by

a short laser pulse
Simulation of impact resistance of
carbon nanotube materials

Temperature distribution in a simulation of

heat transfer in a carbon nanotube material
2

Topics:
From atoms to microstructure: Interatomic
bonding, structure of crystals, crystal defects,
non-crystalline materials.
Mass transfer and atomic mixing: Diffusion,
kinetics of phase transformations.
Mechanical properties, elastic and plastic
deformation, dislocations and strengthening
mechanisms, materials failure.
Phase diagrams: Maps of equilibrium phases.
Polymer structures, properties and applications
of polymers.
Electrical, thermal, magnetic, and optical
properties of materials.

Chapter 1: Introduction
Historical Perspective

Stone Bronze Iron Advanced materials

What is Materials Science and Engineering ?

Processing Structure Properties Performance

Classification of Materials
Metals, Ceramics, Polymers, Semiconductors

Advanced Materials
Electronic materials, superconductors, etc.

Modern Material's Needs, Material of Future

Biodegradable materials, Nanomaterials, Smart materials

Historical Perspective
Beginning of the Material Science - People began to
make tools from stone Start of the Stone Age about
two million years ago.
Natural materials: stone, wood, clay, skins, etc.
The Stone Age ended about 5000 years ago with
introduction of Bronze in the Far East. Bronze is an
alloy (a metal made up of more than one element),
copper + < 25% of tin + other elements.
Bronze: can be hammered or cast into a variety of
shapes, can be made harder by alloying, corrode only
slowly after a surface oxide film forms.
The Iron Age began about 3000 years ago and continues
today. Use of iron and steel, a stronger and cheaper
material changed drastically daily life of a common
person.
Age of Advanced materials: throughout the Iron Age
many new types of materials have been introduced
(ceramic, semiconductors, polymers, composites).
Understanding of the relationship among structure,
properties, processing, and performance of materials.
Intelligent design of new materials.

A better understanding of structure-compositionproperties relations has lead to a remarkable progress

in properties of materials. Example is the dramatic
progress in the strength to density ratio of materials, that
resulted in a wide variety of new products, from dental
materials to tennis racquets.

Figure from: M. A. White, Properties of Materials

(Oxford University Press, 1999)
6

What is Materials Science and Engineering ?

Processing
Materials
Optimization Loop

Structure
Observational

Properties

Material science is the investigation of the relationship

among processing, structure, properties, and performance
of materials.

Structure
Subatomic level (Chapter 2)
Electronic structure of individual
atoms that defines interaction among
atoms (interatomic bonding).

Atomic level (Chapters 2 & 3)

Arrangement of atoms in materials
(for the same atoms can have
different properties, e.g. two forms of
carbon: graphite and diamond)

Microscopic structure (Ch. 4)

Arrangement of small grains of
material that can be identified by
microscopy.

Macroscopic structure
Structural elements that may be
viewed with the naked eye.

Monarch butterfly
~ 0.1 m

Length-scales

Angstrom = 1 = 1/10,000,000,000 meter = 10-10 m

Nanometer = 10 nm = 1/1,000,000,000 meter = 10-9 m

Micrometer = 1m = 1/1,000,000 meter = 10-6 m

Millimeter = 1mm = 1/1,000 meter = 10-3 m
Interatomic distance ~ a few
A human hair is ~ 50 m
Elongated bumps that make up the data track on a CD are
~ 0.5 m wide, minimum 0.83 m long, and 125 nm high

The Scale of Things (DOE)

Things Manmade

Bee
~ 15 mm

1 meter (m)

10-1 m

0.1 m
100 mm

Progress in miniaturization

Monarch butterfly
~ 0.1 m

Cat
~ 0.3 m

100 m

10-2 m

0.01 m
1 cm
10 mm

10-3 m

1 millimeter (mm)

Objects fashioned from

metals, ceramics, glasses, polymers ...
Head of a pin
1-2 mm

Microelectronics
MEMS (MicroElectroMechanical Systems) Devices
10 -100 m wide

The Microworld

Dust mite
300 m

Human hair
~ 50 m wide
Fly ash
~ 10-20 m

10-4 m

0.1 mm
100 m

10-5 m

0.01 mm
10 m
Red blood cells
Pollen grain

Magnetic domains
garnet film
11 m wide stripes

10 nm

Cell membrane

DNA
~2 nm wide
Atoms of silicon
spacing ~tenths of nm

m
cm
mm
m
nm

100
10-2
10-3
10-6
10-9

1m
0.01 m
0.001 m
0.000001 m
0.000000001 m

1 micrometer (m)
Visible
spectrum

The Nanoworld

ATP synthase

Progress in atomic-level understanding

Schematic, central core

meter
centimeter
millimeter
micrometer
nanometer

10-6 m

Red blood cells

with white cell
~ 2-5 m

10-7 m

0.1 m
100 nm

10-8 m

0.01 m
10 nm

Indium arsenide
quantum dot

Quantum dot array -germanium dots on silicon

Biomotor using ATP

10-9 m

10-10 m

Self-assembled
mushroom

1 nanometer (nm)

0.1 nm

MSE 2090: Introduction to Materials Science

The 21st century challenge -- Fashion materials at the nanoscale with desired properties and functionality

Things Natural

Quantum corral of 48 iron atoms on copper surface

positioned one at a time with an STM tip
Corral diameter 14 nm

Chapter 1, Introduction

10

Length and Time Scales in Materials Modeling

by Greg Odegard, NASA

11

1
10-7
10-9

Farid Abraham, IBM

MD of crack propagation

Leonid Zhigilei, UVA

Phase transformation on
diamond surfaces

10-12

Nanoscopic

106
103

10-8

Mo Li, JHU, Atomistic

model of a nanocrystalline

10-9

Time Scale, seconds

Dislocation Dynamics
Nature, 12 February, 1998

di a
n
a
, S ture l
m
l
Ho r frac mode
h
bet anula otts
a
z
i
El tergr arlo P
In te C
n
Mo

Microscopic

1027
Length Scale, number of atoms
109

Mesoscopic

0.1
Length Scale, meters
10-7

Length and Time Scales in Materials Modeling

12

Structure, Processing, & Properties

ex: hardness vs microstructure of steel
P
Properties
ti depend
d
d on microstructure
i
t
t

Processing changes microstructure

ex: microstructure vs cooling rate of steel

(d)

H
Hardnes
ss (BHN
N)

600

1040 steel
0.4 wt. % C steel
BAINITE

500
00

PEARLITE

(c)
30 m

400SPHEROIDITE (b)
(a)

4 m

300
200

30 m

100
0.01 0.1

MARTENSITE

30 m

1
10 100 1000
Cooling Rate (C/s)

Data obtained from Figs. 10.30(a) and 10.32 with 0.4 wt% C composition, and from Fig. 11.14 and
associated discussion, Callister 7e. Micrographs adapted from (a) Fig. 10.19; (b) Fig. 9.30;(c) Fig.
10.33; and (d) Fig. 10.21, Callister 7e.

Chapter 1 - 13

Read this chapter for a general orientation to the MSE field.

An important unifying concept in materials science and engineering

is that there is a direct relationship between a materials processing,
microstructure,
i
t t
properties
ti and
d performance
f

Chapter 1 - 14

Materials have historically defined

the level of societal development
and development of materials with
p
have allowed
new capabilities
major technological advances
Stone Age
Bronze Age
g
Iron Age
Now?
Silicon Age
Composites Age
Biomaterials Age
Requirements
mechanical strength
good lubricity
biocompatibility
bi
tibilit
Chapter 1 - 15

Hip Implant
Key problems to overcome
fixation agent to hold acetabular cup
cup liner material
generation of wear particles could
cause bone cell death
femoral stem fixing agent (glue),
hydroxyapatite
IN THIS EXAMPLE METALS,
CERAMICS AND POLYMERS
ARE USED IN COMBINATION
TO ACHIEVE FUNCTIONALITY
REQUIRING A WIDE RANGE
OF PROPERTIES

Ball

Acetabular
Cup and Liner

Femoral
Stem

Chapter 1 - 16

COMPARISONS OF CLASSES OF MATERIALS

ELASTIC MODULUS (GPa)

IT IS CRITICAL TO HAVE
A GENERAL FEELING
FOR THE BASIC
BEHAVIORS OF THE
DIFFERENT CLASSES
OF MATERIALS

Chapter 1 - 17

COMPARISONS OF CLASSES OF MATERIALS

TENSILE STRENGTH (MPa)

Chapter 1 - 18

COMPARISONS OF CLASSES OF MATERIALS

FRACTURE TOUGHNESS

Chapter 1 - 19

COMPARISONS OF CLASSES OF MATERIALS

ELECTRICAL CONDUCTIVITY

~ 1026 range

Chapter 1 - 20

Bohr Model
The Bohr model assumes electrons move in circular orbits of
radius r about the nucleus and the electrons have
discrete energy states
Electrons have zero energy when they are free and hence
the energy of an electron is negative when it is bound to
an atom.
t
The energy required to remove the electron from the atom is
given by the equation:

E = - 13.6 Z2 eV
n2

Z = atomic number
n = principal quantum
number

For hydrogen,
hydrogen Z = 1 and n = 1,
1 so the single electron
would require 13.6 eV to be removed
Chapter 1 - 21

Bohr Model of an Atom

Since electrons have discrete allowed energy levels, the
transition of an electron to a different energy level requires
either
i h the
h absorption
b
i off energy ((moves to a llarger n)
) or the
h
emission of energy (moves to a lower n)
The value of emitted energy when an electron moves to a lower
principal quantum number shell is also a discrete value that
is characteristic of the element and the shell-to-shell
transition
Analyses of the energies of electrons emitted from an excited
atom would allow identification of the element from which the
electron was emitted; this is the basis for the surface
analytical technique Auger Electron Spectroscopy

Chapter 1 - 22

Quantum Mechanical Model of Atom

Atoms are more complex than the Bohr model, with
electrons having often non-circular orbitals about
the nucleus
Identification of the electronic structure requires four
((n,, l,, m,, s)) quantum
q
numbers:
n, the principal quantum number is the major
determining factor of the energy and must be a
positive integer 1, 2, 3, 4, (sometimes also
identified as K, L, M, N,
l, determines the ways in which the orbital angular
momentum is quantized and varies from 0 for the
s
s subshell; 1 for the p
p subshell; 2 for the d
d
subshell, etc. Electrons in the s subshell have
zero angular momentum and thus have a
spherically symmetric orbit. Higher subshell
electrons have angular momentums and their
orbitals are extended in certain directions.

The orbital describing

the distribution of p
electrons
l t
relative
l ti tto
the nucleus has a
dumbbell shape. Up to
2 electrons can
simultaneously
i lt
l occupy
the shown orbital.
Identical orbitals lie
along the x and y axes.

Chapter 1 - 23

Ionization energies
The following is a list of the first ionization energies for
selected elements
elements, which would create a +1 ion
ARRANGED IN APPROXIMATE LOCATION AS IN PERIODIC TABLE

H 13.6 eV
Li 5.4 eV
Na 5.2 eV

Cs 3.9 eV

C
F
11.2 eV 17.4 eV

He
24.6 e V

Ne
21.6 eV

Chapter 1 - 24

Electronic Structure
Electrons have wavelike and particulate
properties.
properties
This means that electrons are in orbitals defined
by a probability.
Each orbital at discrete energy level determined
by quantum numbers.
Quantum #

Designation

n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)

l = subsidiary (orbitals)
s, p, d, f (0, 1, 2, 3,, n-1)
ml = magnetic
1, 3, 5, 7 (-l to +l)
ms = spin

-
,
Chapter 1 - 25

Electron Energy States

Electrons...

have discrete energy states

tend to occupy
py lowest available energy
gy state.
4d
4p

N-shell n = 4

3d
4s
Energy

3p
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 1 - 26

Specifying Total Electronic Structure

Pauli Exclusion Principle
No two electrons in a given atom can have the same set of
quantum numbers, thus only 1 electron is allowed in each
quantum state

Electrons occupy the lowest available quantum states

Now consider the case of Fe, which has 26 electrons
(next slide)

Chapter 1 - 27

Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2
4d
4p

N-shell n = 4 valence
electrons

3d
4s
Energy

3p
3
3s

M h ll n = 3
M-shell

2p
2
2s

L-shell n = 2

1s

K shell n = 1
K-shell
Chapter 1 - 28

RELATIVE ENERGIES OF ELECTRONS

IN SHELLS AND SUBSHELLS

Chapter 1 - 29

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element
Hydrogen
Helium
Lithium
Beryllium
B
Boron
Carbon
...
Neon
Sodium
Magnesium
Aluminum
...
Argon
...
Krypton

Atomic #
1
2
3
4
5
6

Electron configuration
1s 1
1s 2
(stable)
1s 2 2s 1
1s 2 2s 2
1 2 2s
1s
2 2 2p
2 1
1s 2 2s 2 2p 2
...

10
11
12
13

1s 2 2s 2 2p 6
(stable)
1s 2 2s 2 2p 6 3s 1
1s 2 2s 2 2p 6 3s 2
1s 2 2s 2 2p 6 3s 2 3p 1
...

18
...
36

1s 2 2s 2 2p 6 3s 2 3p 6
(stable)
...
1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

Why? Valence (outer) shell usually not filled completely so

are not at lowest energy.

Chapter 1 - 30

Electron Configurations
Valence electrons are those in unfilled shells
Filled shells more stable
Valence electrons are most available for bonding and
control the chemical, electrical, thermal and optical
properties
example: C (atomic number = 6)
1s2 2s2 2p2
valence electrons
Chapter 1 - 31

The Periodic Table

acccept 2e
e
acccept 1e
e
inert g
gases

give up
p 1e
giive up 2
2e
give up
p 3e

Columns: Similar Valence Structures so similar properties

He

Li Be

F Ne

Na Mg
g

Cl Ar

K Ca Sc
Rb Sr

Cs Ba

Se Br Kr
Te

Xe

Po At Rn

Fr Ra

Electropositive elements:
Readily give up electrons
to become + ions.

Electronegative elements:
Readily acquire electrons
to become - ions.
Chapter 1 - 32

Electronegativity
Capacity to accept electrons to form negative ions

Ranges from 0.7 to 4.0,

Large and small values = very reactive elements

Smaller electronegativity

Larger electronegativity

CHAPTER 2 CONTINUED NEXT LECTURE

Chapter 1 - 33

Broad Classification of Materials

Metals: metallic bonding
strong, high modulus, ductile, medium to high Tmp
high
g thermal and electrical conductivity
y
crystalline, opaque, reflective

Polymers/plastics: covalent and van der Waals bonding

soft, ductile, low strength, low modulus, low density
thermal and electrical insulators
optically translucent or transparent.

Ceramics: ionic and covalent bonding

metallic+non-metallic element compounds (oxides, carbides, etc.)

brittle, crystalline or amorphous, high Tmp
strong, high modulus
electrically and thermally insulating

Chapter 1 - 34

Types of Materials
Let us classify materials according to the way the atoms are
bound together (Chapter 2).
Metals: valence electrons are detached from atoms, and
spread in an 'electron sea' that "glues" the ions together.
Strong, ductile, conduct electricity and heat well, are shiny
if polished.
Semiconductors: the bonding is covalent (electrons are
shared between atoms). Their electrical properties depend
strongly on minute proportions of contaminants. Examples:
Si, Ge, GaAs.
Ceramics: atoms behave like either positive or negative
ions, and are bound by Coulomb forces. They are usually
combinations of metals or semiconductors with oxygen,
nitrogen or carbon (oxides, nitrides, and carbides). Hard,
brittle, insulators. Examples: glass, porcelain.
Polymers: are bound by covalent forces and also by weak
van der Waals forces, and usually based on C and H. They
decompose at moderate temperatures (100 400 C), and
are lightweight. Examples: plastics rubber.

35

Properties
Properties are the way the material responds to the
environment and external forces.
Mechanical properties response to mechanical forces,
strength, etc.
Electrical and magnetic properties - response electrical
and magnetic fields, conductivity, etc.
Thermal properties are related to transmission of heat and
heat capacity.
Optical properties include to absorption, transmission and
scattering of light.
Chemical stability in contact with the environment corrosion resistance.

36

Material Selection
Different materials exhibit different crystal structures
(Chapter 3) and resultant properties

(a)

(b)
force

37

Material Selection
Different materials exhibit different microstructures
(Chapter 4) and resultant properties

Superplastic deformation involves low-stress sliding along

grain boundaries, a complex process of which material
scientists have limited knowledge and that is a subject of
current investigations.
38

Material selection: Properties/performance and cost

metals
ceramics

semiconductors

polymers
39

Composition, Bonding, Crystal Structure

and Microstructure DEFINE Materials Properties
Composition

Bonding

Crystal Structure

Thermomechanical
Processing

Microstructure

40

Future of materials science

Design of materials having specific desired characteristics
directly from our knowledge of atomic structure.
Miniaturization:
Nanostructured" materials, with
microstructure that has length scales between 1 and 100
nanometers
with
unusual
properties.
Electronic
components, materials for quantum computing.
Smart materials: airplane wings that adjust to the air
flow conditions, buildings that stabilize themselves in
earthquakes
Environment-friendly materials: biodegradable or
photodegradable plastics, advances in nuclear waste
processing, etc.
Learning from Nature: shells and biological hard tissue
can be as strong as the most advanced laboratory-produced
ceramics, mollusces produce biocompatible adhesives that
we do not know how to reproduce
Materials for lightweight batteries with high storage
densities, for turbine blades that can operate at 2500C,
room-temperature superconductors? chemical sensors
(artificial nose) of extremely high sensitivity, cotton shirts
that never require ironing
41