MME 2001

MATERIALS SCIENCE 1
13.10.2015
outline
overview of last lecture
periodic table / electronegativity
Classification of elements / interatomic
bonding
Structure of solids:
crystaline vs noncrystalline
Crystal systems;
BCC, FCC, HCP
atomic packing
crystallographic directions, planes
QUIZ (will start at 14:50 p.m. !)
The Periodic Law
Mendeleev realized that:
When arranged by increasing atomic
number, the chemical elements display a
regular and repeating pattern of chemical
and physical properties.
what are these properties?
Metallic vs nonmetallic character
Atomic radius
Ionization energies (energy necessary to remove
the outermost electron from the atom)
Electron affinities (energy change when an
electron is added to a neutral atom)
Reactivity
Electronegativity
Organisation of the periodic table
The vertical columns: groups from 1 to 18.
Elements in the same group have similar valence
electron structures
and hence similar
chemical and
physical
properties.

groups
Organisation of the periodic table
elements are situated, with increasing atomic
number, in seven horizontal rows
called periods.
Each contains
elements with
electrons in the
Same outer shell.

periods
Periodic table
 Periodic Table
metallic character
Atomic radii

Negative electron affinity

nonmetallic character
metallic character

onization energy
Atomic radii

nonmetallic character
onization energy
Negative electron affinity
Ionization Energy
IE = energy required to remove an
electron from an atom in the gas phase.

Mg (g) + 738 kJ ---> Mg+ (g) + e-

Electronegativity
the tendency of an atom to attract electrons
towards itself.
Atoms are more likely to accept electrons if their
outer shells are almost full, and if they are less
shielded from (i.e., closer to) the nucleus.

electronegativity
increases!
Electronegativity
Electronegativity
Metals, Nonmetals & Metalloids
1

2
Nonmetals
3

5
Metals
6

7
Metalloids
Metals
88 elements are metals or metal like element
Physical properties:
good conductors of heat and electricity
shiny
ductile (can be stretched into thin wires)
malleable (can be pounded into thin sheets)
High density (heavy for their size)
High melting point
chemical properties:
Easily lose electrons
Form positive (+) ions
Corrode easily
Non-metals
Their characteristics are opposite to those of metals.
Physical Properties of Nonmetals:
No luster (dull appearance)
Poor conductor of heat and electricity
Brittle (breaks easily)
Not ductile
Not malleable
Low density
Low melting point
Many non-metals are gases.
Non-metals
Chemical Properties of Non-metals:
Tend to gain electrons
metals that tend to lose electrons but nonmetals
that tend to gain electrons, to form compounds
with each other.
These compounds are called
ionic compounds.
When two or more
nonmetals bond with
each other, they form
a covalent compound.
Metalloids
Metalloids (metal-like) have properties of both
metals and non-metals.
They are solids
can be shiny or dull
They conduct heat
and electricity better
than non-metals but
not as well as metals
They are ductile and
malleable
interatomic bonding
the bonding involves the valence electrons
the nature of the bond depends on the electron
structures of the constituent atoms.
There are three types of bonding: each bonding
type arises from the tendency of the atoms to
assume stable electron structures.
Secondary or physical forces and energies are
weaker than the primary ones, but nonetheless
influence the physical properties of some
materials.
interatomic bonding
Ionic
Metal (cation) with non-metal (anion)
Transfer of electron(s)
Strong bond high melting point
Covalent
Non-metal with non-metal
Sharing of electron(s)
Non-polar (equal distribution of electrons)

Polar (uneven electron distribution)

Weak bondslow melting points

Metallic (nuclei in a sea of shared electrons)
ionic bonding
Forms between metallic and nonmetallic
elements; elements at the horizontal extremities
of the periodic table.
a metallic atom easily gives up its valence
electrons to the nonmetallic atoms.
In the process all the atoms acquire stable
configurations and become ions.
Ionic bonding is non-directional (magnitude of the
bond is equal in all directions around the ion)
Ceramic materials exhibit ionic bonding
Ionic Bonding
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.

Na (metal) Cl (nonmetal)
Unstable Unstable
electron
11 electrons 17 electrons

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
positive and negative ions, by virtue of their net
electrical charge, attract one another
Ionic Bonding - examples
Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Ion Sizes
+
Forming
Li,152 pm Li + , 78 pm a cation.
3e and 3p e 2e and 3 p

CATIONS are SMALLER than the atoms from

which they come.
The electron/proton attraction has gone UP
and so size DECREASES.
Ion Sizes
-
Forming
F, 71 pm F- , 133 pm an anion.
9e and 9p + e 10 e and 9 p

ANIONS are LARGER than the atoms from

which they come.
The electron/proton attraction has gone DOWN
and so size INCREASES.
Trends in ion sizes are the same as atom sizes.
ionic bonding
The predominant bonding in ceramic materials
is ionic.
Ionic materials are characteristically hard and
brittle and, electrically and thermally
insulative.
These properties are directly related to
electron configurations and/or the nature of the
ionic bond.
 covalent bonding
stable electron configurations are assumed by the
sharing of electrons between adjacent atoms.
Two atoms that are covalently bonded will each
contribute at least one electron to the bond, and
the shared electrons may be considered to belong
to both atoms.
The covalent bond is directional; it is between
specific atoms and may exist only in the direction
between one atom and another that participates
in the electron sharing.
Covalent Bonding
similar electronegativity share electrons
bonds are determined by valence
s & p orbitals dominate bonding
Example: CH4 shared electrons
CH 4
H of carbon atom
C: has 4 valence e-, H

needs 4 more H C H H: C : H
H: has 1 valence e-,
H
needs 1 more
Electronegativities H shared electrons
are comparable. of hydrogen atom
covalent bonding
Covalent bonds may be very strong, as in
diamond, which is very hard and has a very high
melting temperature, 3550 C, or they may be
very weak, as with bismuth, which melts at about
270 C.
Polymeric materials typify this bond, the basic
molecular structure often being a long chain of
carbon atoms that are covalently bonded together
with two of their available four bonds per atom.
The remaining two bonds normally are shared
with other atoms, which also covalently bond.
covalent bonding
interatomic bonds may be partially ionic and
partially covalent.
very few compounds exhibit pure ionic or covalent
bonding.
the degree of either bond type depends on the
relative positions of the components in the periodic
table or the difference in their electronegativities.
The wider the separation (the greater the difference
in electronegativity), the more ionic the bond.
the closer they are (the smaller the difference in
electronegativity), the greater the degree of
covalency.
interatomic bonding
No electronegativity difference between two
atoms leads to a purely non-polar covalent bond.
A B
A small electronegativity difference leads to a
polar covalent bond.
A B
A large electronegativity difference leads to an
ionic bond.
metallic bonding
Metallic materials have one, two, or at most,
three valence electrons.
these valence electrons are more or less free to
drift throughout the entire metal and form a sea
of electrons.
the metallic bond is nondirectional in character.
The free electrons act as a glue to hold the ion
cores together.
Bonding may be weak or strong; bonding energy 68
kJ/mol (0.7 eV/atom) for mercury and 849 kJ/mol
(8.8 eV/atom) for tungsten. Their respective
melting temperatures are 39 and 3410 C.
metallic bonding
Secondary-van der waals-bonding
Secondary, van der Waals, or physical bonds are
weak in comparison to the primary or chemical
ones; bonding energies are typically on the order
of only 10 kJ/mol (0.1 eV/atom).
Secondary bonding exists between virtually all
atoms or molecules, but its presence may be
obscured if any of the three primary bonding types
is present.
Secondary bonding is evidenced for the inert gases,
which have stable electron structures, and, in
addition, between molecules in molecular
structures that are covalently bonded.
Properties linked with bonding
if the bond energy is higher,
Melting point is higher
Thermal expansion
coefficient is smaller Energy
Elastic modulus is
higher
ro
r
Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): high Tm
high E
small
Metals Variable bond energy
(Metallic bonding): moderate Tm
moderate E
moderate
Polymers Directional Properties
(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
high
structure of solids
Energy and Packing
Non dense, random packing Energy
typical neighbour
bond length
typical neighbour r
bond energy

Dense, ordered packing Energy

typical neighbour
bond length
typical neighbour r
bond energy

Dense, ordered packed

structures tend to have lower energies!
Materials and Packing
Crystalline materials:
atoms are situated in a
repeating array over large crystalline SiO2
atomic distances; Si Oxygen
long-range order exists..
each atom is bonded to its
nearest-neighbor atoms.
typical of:
metals
many ceramics
some polymers
noncrystalline solids
noncrystalline materials:
no periodic packing of atoms noncrystalline SiO2
occurs in the case of Si Oxygen
complex structures
rapid solidification

amorphous = noncrystalline

many polymers
some ceramics
? metallic glasses
Materials and Packing
crystalline SiO2
Si Oxygen

noncrystalline SiO2
noncrystalline solids
crystalline vs amorphous solid
depends on the ease with which a random
atomic structure in the liquid can transform to
an ordered state during solidification.
Therefore, amorphous materials are
characterized by atomic or molecular structures
that are relatively complex and become
ordered only with some difficulty.
noncrystalline solids
rapid cooling through the freezing temperature
noncrystalline solid / no time for ordering!
metals normally form crystalline solids
some ceramic materials are crystalline, whereas
others, the inorganic glasses, are amorphous.
polymers may be completely noncrystalline and
semicrystalline consisting of varying degrees of
crystallinity.
noncrystalline solids
T

metals

crystalline

dT/dt
noncrystalline
t
noncrystalline solids
T
ceramics

crystalline

dT/dt

noncrystalline

t
Structure of solids
issues of interest
How do atoms assemble into solid
structures? (we shall focus on metals for
the time being!)
How does the density of a material depend
on its structure?
When do material properties vary with the
sample (i.e., part) orientation?
Structures of crystalline solids
properties of crystalline solids depend on the
crystal structure of the material, the manner in
which atoms are spatially arranged.
For example, magnesium, having one crystal
structure, is much more brittle (i.e., fracture at
lower degrees of deformation) than aluminium
that has yet another crystal structure.
Structure mechanical properties

aluminium

magnesium
structure physical properties
significant property differences exist between
crystalline and noncrystalline materials having
the same composition.
For example, noncrystalline ceramics and
polymers normally are optically transparent; the
same materials in crystalline form tend to be
opaque or, at best, translucent.

Alumina
Single crystal
Polycrystal-low porosity
high porosity
structure of crystalline solids
atomic hard-sphere model: atoms (or ions) are
thought of as being solid spheres having well-
defined diameters. These spheres touch one
another.
the unit cell is the basic structural unit or
building block of the crystal structure and
defines the crystal structure by virtue of its
geometry and the atom positions.
metallic crystal structures
metallic bonding
nondirectional: minimal restrictions as to the
number and position of nearest-neighbor atoms
hence, relatively large numbers of nearest
neighbors
three relatively simple crystal structures are
found for most of the common metals:
face centered cubic (FCC)
body-centered cubic (BCC)
hexagonal close-packed (HCP)
metallic crystal structures
tend to be densely packed.
Reasons for dense packing:
Typically, only one element is present, so all
atomic radii are the same.
bonding is not directional.
nearest neighbor distances tend to be small in
order to reduce bond energy (energy minimization).
electron cloud shields cores from each other
have the simplest crystal structures.
metallic crystal structures
crystal systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
The unit cell geometry is completely defined in
terms of six lattice parameters
edge lengths: a, b, and c
(lattice constants)
interaxial angles:
, , and (lattice angles)

There are seven different

possible combinations of
a, b, and c, and , and
crystal systems
7 distinct crystal systems
cubic
tetragonal
hexagonal
orthorhombic
rhombohedral
monoclinic
triclinic

14 crystal lattices
crystal systems
cubic: a=b=c, ===90

simple body-centered face-centered

cubic cubic (BCC) cubic (FCC)
tetragonal: a=bc, ===90

simple body-centered
tetragonal tetragonal (BCT)
crystal systems
orthorombic: abc, ===90

simple body-centered base-centered face-centered

monoclinic: abc, ==90

simple base-centered
monoclinic monoclinic
 crystal systems

rhombohedral hexagonal triclinic

a=b=c, a=bc, abc,
==90 ==90 =120 90

Total of 14 Bravais lattices!

crystal systems

cubic triclinic
a=b=c abc
===90 90

maximum symmetry minimum symmetry

metallic crystal structures
How can we stack metal atoms to minimize
empty space?
2-dimensions

vs
cube
6 faces
8 corners
12 edges
metallic crystal structures
F.C.C. Crystal structure:

hard-sphere unit cell

reduced-sphere unit cell
aggregate of many atoms
simple cubic structure (SC)
Rare due to low packing density
(only Po has this structure)
Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)
simple cubic (SC) structure
Atoms touch each other along cube edges.
each of 8 corner atoms is shared by eight unit
cells:
8 x (1/8) = 1 atom/unit cell

a = 2R
unit cell
volume = a3 = 8R3
BCC crystal structure
unit cell has cubic geometry
atoms are located at the corners of the cube.
Some of the materials that have a bcc structure
include lithium, sodium, potassium, chromium,
barium, vanadium, alpha-iron and tungsten.
Metals which have a BCC structure are usually
harder and less malleable than close-packed
metals such as copper and gold.
When the metal is deformed, the planes of
atoms must slip over each other, and this is more
difficult in the bcc structure.
Body Centered Cubic Structure (BCC)
8 7
6
5
4 3
1 2

Coordination # = 8
Atomic packing of
an BCC (110)
plane.
body centred cubic (BCC) structure
Atoms touch each other along cube diagonals.
each of 8 corner atoms is shared by eight unit
cells; single center atom is wholly owned:
8 x (1/8) + 1 = 1 + 1 = 2 atoms/unit cell
each center atom touches eight corner atoms:
8 nearest neighbors

2.a 3.a = 4R
FCC crystal structure
unit cell has cubic geometry
atoms are located at the corners and the
centers of all the cube faces.
familiar metals with FCC crystal structure
copper
aluminium
silver
gold
Atomic arrangements - FCC
Reduced sphere FCC unit cell with the (110) plane.
Atomic packing of an FCC (110) plane.

Atoms touch each other along face diagonals.

Face Centered Cubic Structure (FCC)
The face-centered atom in the front face is in contact
with four corner atoms and four other face-centered
atoms behind it (two sides, top and bottom) and is
also touching four face-centered atoms of the unit
cell in front of it.
Coordination # = 12
FCC crystal structure
atoms touch one another across
a face diagonal; cube edge length
a and the atomic radius R

a2 + a2 = (R+2R+R)2
2a2 = (4R)2 = 16R2
R
a2 = 8R2 2R
a
a = 2R2 R
R = a /(22)
FCC crystal structure
each of 8 corner atoms is shared by eight unit cells;
each of 6 face-centered atoms belongs to only two.
8 x (1/8) + 6 x (1/2) = 1 + 3 = 4 atoms/unit cell

The volume of the unit cell,

a3 = (2R2)3 = 16R32

4R=2.a
(a = 2R2)
cubic crystal structures
Xtal structure Coordination # Atoms/unit cell
simple cubic 6 1
body centred 8 2
face centred 12 4
atomic packing factor (APF)
APF is the sum of the sphere volumes of all
atoms within a unit cell divided by the unit
cell volume:

the maximum packing possible for spheres

all having the same diameter.
Atomic Packing Factor (APF)-SC
Volume of atoms in unit cell
APF = Volume of unit cell
volume
atoms atom
4
(0.5a) 3
a
unit cell 1
R=0.5a 3
APF =
a3 volume
close-packed directions unit cell

contains
1
8 x 1/8 = 1 atom/unit cell
APF for a simple cubic structure = 0.52
Atomic Packing Factor: BCC
4R 3a

2a 2a
R
a
Close-packed directions:
length = 4R = 3 a
atoms 4 volume
3
unit cell 2 ( 3a/4) atom
3
APF = APF(BCC)= 0.68
volume
a3
unit cell
Atomic Packing Factor: FCC
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a

atoms volume
4 3 atom
unit cell 4 p ( 2a/4)
3 maximum
APF = = 0.74 achievable APF
a3 volume
unit cell
Closed packed crystal structures
A portion of
a close-packed
plane of
atoms; A, B, and
C positions
are indicated.
The AB
stacking
sequence for
close packed
atomic planes.
Hexagonal close packed (HCP)
crystal structure
Not all metals have unit cells with cubic symmetry;
some common metals have a hexagonal structure
Closed packed crystal structures
The real distinction
between FCC and HCP
lies in where
the third close-packed
layer is positioned.
For HCP, the centers
of this layer are
aligned directly above
the original A
positions.
stacking sequence,
ABABAB ...,
Atomic alignment repeats every other plane!
Closed packed crystal structures
These planes are of the (111) type
For FCC
structure,
the centers
of the third
plane are
situated
over the C
sites of the
first plane.
This yields an ABCABCABC . . . stacking sequence;
the atomic alignment repeats every third plane.
FCC Stacking Sequence
ABCABC... Stacking Sequence
2D Projection
B B
C
A sites A
B B B
B sites C C
C sites B B

A
B
C

FCC Unit Cell

Hexagonal close packed (HCP)
crystal structure
The HCP metals: Cd, Mg, Ti, and Zn.
top and bottom faces consist of six atoms that
form regular hexagons and surround a single atom
in the center.
Another plane that provides three additional
atoms to the unit cell is situated between the top
and bottom planes. The atoms in this mid-plane
have as nearest neighbors atoms in both of the
adjacent two planes.
Hexagonal close packed (HCP)
crystal structure
The equivalent of six atoms is contained in
each unit cell
one-sixth of each of the 12 top and bottom
face corner atoms, one-half of each of the
2 center face atoms, and all 3 midplane
interior atoms.:
12 x 1/6 + 2 x + 3 = 2 +1 + 3 = 6
corner face midplane
Closed packed crystal structures
both FCC and HCP crystal structures have
atomic packing factors of 0.74, which is
the most efficient packing of equal-sized
spheres or atoms.
these two crystal structures may be
described in terms of close-packed planes
of atoms (i.e., planes having a maximum
atom or sphere packing density)
Hexagonal Close-Packed Structure (HCP)
ABAB... Stacking Sequence
3D Projection 2D Projection

A sites Top layer

c B sites Middle layer
A sites
a Bottom layer

Coordination # = 12
6 atoms/unit cell
APF = 0.74
ex: Cd, Mg, Ti, Zn
c/a = 1.633
Unit cell volume

Sin 60 = h /a h = a sin 60
Atomic packing factor

2R=a; R=a/2
ideal c/a ratio in HCP

h2= a2+(a/2)2
a/2 x=(2/3)h
x2 + (c/2)2 = a2
see you next week!