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Chapter 4: Structures of Crystalline Solids: Issues To Address..
Chapter 4: Structures of Crystalline Solids: Issues To Address..
ISSUES TO ADDRESS...
• How do atoms assemble into solid structures
in metallic, ceramic and polymeric materials?
• How do the structures of ceramic materials
differ from those of metals?
vs.
Chapter 4 - 3
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)
2a
From
Fig. 4.2(a)
Callister’s Materials Close-packed directions:
Science and R length = 4R = 3 a
Engineering,
Adapted Version.
a
atoms volume
4
unit cell 2 ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell Chapter 4 - 7
Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
A
• FCC Unit Cell B
C
Chapter 4 - 10
Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection
nA
=
VC NA
Chapter 4 - 12
Theoretical Density,
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol Chapter 4 - 13
Densities of Material Classes
In general Metals/
Graphite/
Composites/
metals > ceramics > polymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? Platinum *GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
(g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
a 2
LD 3.5 nm 1
length 2a
Chapter 4 - 15
Atomic Packing of Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.
Chapter 4 - 16
Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit
(100) 4 3
a R
3
atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 10 19
area a2 4 3 nm 2
m2
R
2D repeat unit 3 Chapter 4 - 17
Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell
2a atoms in plane
atoms above plane
nit
atoms below plane
u
eat
ep
3
h a
r
2D 2
2
4 3 16 3 2
area 2 ah 3 a 3
2
R R
atoms 3 3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
nm 2
m2
R
2D repeat unit 3
Chapter 4 - 18
Section 4.9 – Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538ºC
BCC -Fe
carbon
diamond, graphite 1394ºC
FCC -Fe
912ºC
BCC -Fe
Chapter 4 - 19
Ceramic Crystal Structures
Oxide structures
– oxygen anions much larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations in the holes of the oxygen lattice
Chapter 4 - 20
Site Selection
Which sites will cations occupy?
1. Size of sites
– does the cation fit in the site
2. Stoichiometry
– if all of one type of site is full the
remainder have to go into other types of
sites.
3. Bond Hybridization
Chapter 4 - 21
Ionic Bonding & Structure
1. Size - Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - - From Fig. 4.10
+ + + Callister’s Materials
- - - - - -
Science and Engineering,
Adapted Version.
2ranion 2rcation 2a
a 2ranion
rcation
0.414
ranion
Chapter 4 - 24
Site Selection II
2. Stoichiometry
– If all of one type of site is full the remainder have to go
into other types of sites.
Chapter 4 - 25
Site Selection III
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
rMg/rO = 0.514
Chapter 4 - 29
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
rCs 0.170
0.939
rCl 0.181
• antifluorite structure –
cations and anions
reversed
From Fig. 4.14
Callister’s Materials Science and Engineering
Adapted Version.
Chapter 4 - 32
ABX3 Crystal Structures
Perovskite structure
Chapter 4 - 33
Mechanical Properties
We know that ceramics are more brittle
than metals. Why?
• Consider method of deformation (will
learn later in chapters on mechanical
properties – Chapter 9 and 10)
– slippage along slip planes
• in ionic solids this slippage is very difficult
• too much energy needed to move one anion
past another anion
Chapter 4 - 34
Ceramic Density Computation
Number of formula units/unit cell
Chapter 4 - 35
Silicate Ceramics
Most common elements on earth are Si & O
Si4+
O2-
Chapter 4 - 37
Silica Glass
Chapter 4 - 38
Silicates
• (Si2O5)2-
From Fig. 4.22
• So need cations to balance Callister’s Materials Science and
Engineering, Adapted Version.
charge
Chapter 4 - 40
Layered Silicates
• Kaolinite clay alternates (Si2O5)2- layer with
Al2(OH)42+ layer
Chapter 4 - 42
Carbon Forms
• Carbon black – amorphous
– surface area ca. 1000 m2/g
• Diamond
– tetrahedral carbon
• hard – no good slip planes
• brittle – can cut it
– large diamonds – jewelry
– small diamonds
• often man made - used for
cutting tools and polishing
– diamond films
• hard surface coat – tools, From Fig. 4.24
Callister’s Materials Science and Engineering
medical devices, etc. Adapted Version.
Chapter 4 - 43
Carbon Forms - Graphite
• layer structure – aromatic layers
Chapter 4 - 44
Carbon Forms –
Fullerenes and Nanotubes
• Fullerenes or carbon nanotubes
– wrap the graphite sheet by curving into ball or tube
– Buckminister fullerenes
• Like a soccer ball C60 - also C70 + others
10 nm
• % Crystallinity: % of material
that is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases. amorphous
region
From Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.) Chapter 4 - 47
Polymer Crystal Forms
• Single crystals – only if slow careful growth
Spherulite
surface
Chapter 4 - 49
Spherulites – crossed polarizers
Maltese cross
”
r
co s
“1
X-
m ys reflections must
in a
g -r be in phase for
”
“2
“1 X a detectable signal From Fig. 4.35
” g Callister’s Materials
extra
oi
n
“2
Measurement of X-ray
intensity n
critical angle, c, d
(from 2 sin c
allows computation of
detector)
planar spacing, d.
c
Chapter 4 - 52
X-Ray Diffraction Pattern
z z z
c c c
y (110) y y
a b a b a b
Intensity (relative)
x x x (211)
(200)
Diffraction angle 2
Chapter 4 - 53
SUMMARY
• Common metallic crystal structures are FCC, BCC, and
Chapter 4 - 54
SUMMARY
• Ceramic materials have covalent & ionic bonding.
Chapter 4 - 55
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 4 - 56