MSE 201 Introduction to NCSU

Nano-Materials Science

Instructor: Dr. Gerd Duscher

http://volweb.utk.edu/~gduscher
email: [email protected]

Office: 421 Ferris Hall

Office Hours: Online: Friday 1pm-2pm?

TA Office Hours: Monday 2pm-3pm?

 Book
Any Edition will do but this si the current one:
 Summary: Primary Bonds
Ceramics large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers directional Properties

(Covalent & Secondary): van der Waals bonding dominates
small T
small E
large 
 Energy And Packing
• Non dense, random packing

energy
typical neighbor
bond length

typical neighbor r
bond energy

• Dense, regular packing

energy
typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular-packed structures tend to have

lower energy.
 CHAPTER 3:
Crystal Structures & Properties
ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample orientation?
 Materials And Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
 Metallic Crystals
• tend to be densely packed.
• have several reasons for dense packing:
-Typically, only one element is present, so all atomic
radii are the same.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.

• have the simplest crystal structures.

We will look at three such structures...

 Simple Cubic Structure (sc)
• rare due to poor packing (only Po has this structure)
• close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)
 Atomic Packing Factor
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1  (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
 Body Centered Cubic Structure (bcc)

• Close packed directions are cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8
 Atomic Packing Factor: bcc
• APF for a body-centered cubic structure = 0.68

Close-packed directions:
length = 4R
= 3a
Unit cell contains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
a
atoms volume
4
unit cell 2  ( 3a/4 ) 3
3 atom
APF =
volume
a3
unit cell
Face Centered Cubic Structure (fcc)
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12
 Atomic Packing Factor: fcc
• APF for a body-centered cubic structure = 0.74

Close-packed directions:
length = 4R
= 2a
Unit cell contains
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4
unit cell 4  ( 2a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 fcc Stacking Sequence
• ABCABC... stacking sequence
• 2D projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

• fcc unit cell

Hexagonal Close-Packed Structure (hcp)

• ABAB... Stacking Sequence

• 3D Projection • 2D Projection

A sites

B sites

A sites

• Coordination # = 12
• APF = 0.74

12
 Hexagonal Close-Packed Structure (hcp)
graphite
 Diamond Structure

silicon, diamond ZnS – type (GaAs)

 Structure Of Compounds: Nacl
• Compounds: Often have similar close-packed structures.
• Structure of NaCl • Close-packed directions
--along cube edges.
 Perovskite Strucutre

SrTiO3

Applications: non-linear resistors (PTC), SMD capacitors,

piezoelectric sensors and actuators, ferroelectric memory.
 Theoretical Density, 
# atoms/unit cell atomic weight (g/mol)
nA
=
volume/unit cell Vc N A avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)
 Characteristics of Selected Elements at 20 ºC

At. Weight Density Crystal AtomicRadius

Element Symbol (amu) (g/cm 3 ) Structure (nm)
Aluminum Al 26.98 2.71 fcc 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 bcc 0.217
Beryllium Be 9.012 1.85 hcp 0.114
Boron B 10.81 2.34 rhomb ------
Bromine Br 79.90 ------ ------ ------
Cadmium Cd 112.41 8.65 hcp 0.149
Calcium Ca 40.08 1.55 fcc 0.197
Carbon C 12.011 2.25 hex 0.071
Cesium Cs 132.91 1.87 bcc 0.265
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 bcc 0.125
Cobalt Co 58.93 8.9 hcp 0.125
Copper Cu 63.55 8.94 fcc 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 ortho. 0.122
Germanium Ge 72.59 5.32 dia. cubic 0.122
Gold Au 196.97 19.32 fcc 0.144
 Theoretical Density, 
# atoms/unit cell Atomic weight (g/mol)
nA
=
Volume/unit cell Vc N A Avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see next slide):
• crystal structure = fcc: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10-7 cm)
Vc = a3 ; for fcc, a = 4R/ 2 ; Vc = 4.75 x 10-23 cm3
Result: theoretical Cu = 8.89 g/cm3
compare to actual: Cu = 8.94 g/cm3
 Densities Of Material Classes
metals ceramics polymers Metals/
Graphite/
Ceramics/ Polymers
Composites/
Alloys fibers
Semicond
Why? 30
Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).

• large atomic mass Steels

 (g/cm 3)
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
• less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass-soda
Concrete
Glass fibers
Silicon PTFE
• often lighter elements 2 Magnesium Graphite
GFRE*
Carbon fibers
Silicone CFRE*
Polymers have... PVC
PET
Aramid fibers
AFRE*
• poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
• lighter elements (C,H,O) 0.5 Wood
Composites have... 0.4
0.3
• intermediate values
 Crystals as Building Blocks

• Some engineering applications require single crystals:

--diamond single --turbine blades
crystals for abrasives

• Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.
 POLYCRYSTALS
• Most engineering materials are polycrystals.

1 mm

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
-properties vary with
direction: anisotropic.
-example: the modulus
of elasticity (E) in bcc iron:
E (edge) = 125 GPa
• Polycrystals
-properties may/may not 200 mm
vary with direction.
-if grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-if grains are textured,
anisotropic.
Crystallographic Directions
z [001]

[111]

[112] y
a0/2

[110]
x
 Crystallographic Directions
z x y z
Projection
Projection
Reduction

Result:
y Enclosure [ ]

x
 Crystallographic Planes
z plane (001)

plane (011)

a0/2 y

plane (112)
x
Crystallographic Planes
Crystallographic Planes
 Crystallographic Planes
z x y z
Projection
Projection
Reciprocals
Reduction

y Result:
Enclosure ( )

x
 Crystallographic Planes
1/3
z x y z
Projection
Projection
Reciprocals
Reduction
1/2

y Result:
Enclosure ( )

x
Crystallographic Planes
1/3
x y z
Projection
y
Projection
Reciprocals
Reduction
1/2
x
Result:
Enclosure ( )