SUMMARY: BONDING

Type Bond Energy Comments

Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular
 PROPERTIES FROM BONDING: TM
• Bond length, r • Melting Temperature, Tm
F
F

• Bond energy, Eo

Tm is larger if Eo is larger.
 PROPERTIES FROM BONDING: E
• Elastic modulus, E
Elastic modulus

F L
=E
Ao Lo

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus

 PROPERTIES FROM BONDING: a
• Coefficient of thermal expansion, a
coeff. thermal expansion

L
= a(T2-T1)
Lo

• a ~ symmetry at ro

a is larger if Eo is smaller.
 SUMMARY: PRIMARY BONDS
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large a
CHAPTER 3: Structures of Metals
and Ceramics

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?

• How do the structures of ceramic

materials differ from those of metals?

• How does the density of a material depend on

its structure?
• When do material properties vary with the
sample (i.e., part) orientation?

1
 ENERGY AND PACKING
• Non dense, random packing

• Dense, regular packing

Dense, regular-packed structures tend to have

lower energy.
2
 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. 74 elements

have the simplest crystal structures – BCC, FCC
and HCP

We will look at three such structures...

3
 The crystal lattice

A point lattice is made up of regular,

repeating points in space. An atom or
group of atoms are tied to each lattice
point
14 different point lattices, called Bravais lattices, make up the crystal system.
The lengths of the sides, a, b, and c, and the angles between them can vary for
a particular unit cell.
Three simple lattices that describe metals are Face Centered Cubic (FCC) Body
Centered Cubic (BCC) and Hexagonal Close Packed (HCP)
 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

Click on image to animate

(Courtesy P.M. Anderson)

4
 ATOMIC PACKING FACTOR

• APF for a simple cubic structure = 0.52

Adapted from Fig. 3.19,

Callister 6e. 5
 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

Adapted from Fig. 3.1(a),

Click on image to animate Callister 6e.

(Courtesy P.M. Anderson)

6
 ATOMIC PACKING FACTOR: FCC
• APF for a body-centered cubic structure = 0.74

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e.

7
 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

Adapted from Fig. 3.2,

Click on image to animate Callister 6e.

(Courtesy P.M. Anderson) 8

 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e.

9
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites

B sites

A sites
Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
• APF = 0.74

10
 THEORETICAL DENSITY, 

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 -7cm)

Result: theoretical Cu = 8.89 g/cm 3

Compare to actual: Cu = 8.94 g/cm3
11
Characteristics of Selected Elements at 20C
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ teristics of
Cadmium Cd 112.41 8.65 0.149 Selected
Calcium Ca 40.08 1.55 0.197 Elements",
inside front
Carbon C 12.011 2.25 0.071 cover,
Cesium Cs 132.91 1.87 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------ 12
 DENSITIES OF MATERIAL
CLASSES
metals• ceramics• polymers
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values Data from Table B1, Callister 6e.
13
 CERAMIC BONDING
• Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University. 14
 IONIC BONDING & STRUCTURE
• Charge Neutrality:
--Net charge in the
structure should
be zero.

--General form:

• Stable structures:
--maximize the # of nearest oppositely charged neighbors.

Adapted from Fig. 12.1,

Callister 6e.

15
 COORDINATION # AND IONIC
•
RADII
Coordination # increases with
Issue: How many anions can you
arrange around a cation?

Adapted from Fig. 12.4,

Callister 6e.

Adapted from Fig. 12.2,

Callister 6e.

Adapted from Fig. 12.3,

Adapted from Table Callister 6e.
12.2, Callister 6e.
16
 EX: PREDICTING STRUCTURE OF
FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation • Answer:
Al3+ r cation 0.077
Fe 2+ 
r anion 0.140
Fe 3+  0.550
Ca2+
based on this ratio,
--coord # = 6
Anion
--structure = NaCl
O2-
Cl-
F-
Data from Table 12.3,
Callister 6e.
17
 AmXp STRUCTURES
r cation 0.100
• Consider CaF2 :   0.8
r anion 0.133
• Based on this ratio, coord # = 8 and structure = CsCl.
• Result: CsCl structure w/only half the cation sites
occupied.
• Only half the cation sites
are occupied since
#Ca2+ ions = 1/2 # F- ions.

Adapted from Fig. 12.5,

Callister 6e.

18
 DEMO: HEATING AND
COOLING OF AN IRON WIRE
The same atoms can
• Demonstrates "polymorphism" have more than one
crystal structure.

19
 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

20
STRUCTURE OF COMPOUNDS: NaCl
• Compounds: Often have similar close-packed structures.
• Structure of NaCl • Close-packed directions
--along cube edges.

Click on image to animate Click on image to animate

(Courtesy P.M. Anderson) (Courtesy P.M. Anderson)

21
Diamond, BeO and GaAs are examples of FCC structures with two atoms per lattice
point
 CRYSTALS AS BUILDING
BLOCKS
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.30(c), Callister 6e.
(Fig. 8.30(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used
with permission.)

• Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.

(Courtesy P.M. Anderson)

22
 POLYCRYSTALS
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
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).
23
 SINGLE VS POLYCRYSTALS
• Single Crystals
Data from Table 3.3,
-Properties vary with Callister 6e.
(Source of data is
direction: anisotropic. R.W. Hertzberg,
Deformation and
-Example: the modulus Fracture Mechanics of
Engineering Materials,
of elasticity (E) in BCC iron: 3rd ed., John Wiley
and Sons, 1989.)

• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
4.12(b), Callister 6e.
vary with direction. (Fig. 4.12(b) is
courtesy of L.C. Smith
-If grains are randomly and C. Brady, the
National Bureau of
oriented: isotropic. Standards,
Washington, DC [now
(Epoly iron = 210 GPa) the National Institute
-If grains are textured, of Standards and
Technology,
anisotropic. Gaithersburg, MD].)

24
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.

26
 GLASS STRUCTURE
• Basic Unit: • Glass is amorphous
4- • Amorphous structure
Si0 4 tetrahedron occurs by adding impurities
Si4+ (Na+,Mg2+,Ca2+, Al3+)
O2-
• Impurities:
interfere with formation of
crystalline structure.

• Quartz is crystalline
SiO2:

(soda glass)
Adapted from Fig. 12.11,
Callister, 6e.

28
 SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.
• We can predict the density of a material,
provided we know the atomic weight, atomic
radius, and crystal geometry (e.g., FCC,
BCC, HCP).
• Material properties generally vary with single
crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains.

27
Ceramic Their Properties and
Material Behavior
Engr 2110
Dr. R. Lindeke
 Taxonomy of Ceramics
Glasses Clay Refractories Abrasives Cements Advanced
products ceramics
-optical -whiteware -bricks for -sandpaper -composites engine
-composite -bricks high T -cutting -structural -rotors
reinforce (furnaces) -polishing -valves
-containers/ Adapted from Fig. 13.1 and discussion in
-bearings
household Section 13.2-6, Callister 7e.
-sensors
• Properties:
-- Tm for glass is moderate, but large for other ceramics.
-- Small toughness, ductility; large moduli & creep resist.
• Applications:
-- High T, wear resistant, novel uses from charge neutrality.
• Fabrication
-- some glasses can be easily formed
-- other ceramics can not be formed or cast.
 Ceramic Bonding
• Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity (remember!?!).
• Large vs small ionic bond character:
CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University.
 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
• The same ideas apply to all “ceramics”
• Principles of Ceramic Architecture:
– Size relationships Cation to Anion
– Electrical Neutrality of the overall structure
– Crystallographic Arrangements
– Stoichiometry Must Match
 Silica Glass

• A “Dense form” of amorphous silica

– Charge imbalance corrected with “counter
cations” such as Na+
– Borosilicate glass is the pyrex glass used
in labs
• better temperature stability & less brittle than sodium
glass
GLASSES – transparent and easily shaped
Noncrystalline Silicates + oxides (CaO, Na2O, K2O, Al2O3)
E.g. Soda lime glass = 70wt% SiO2 + 30% [Na2O (soda) and CaO(lime)
Table 13.1
 GLASS PROPERTIES
• Specific volume (1/) vs Temperature (T):
• Crystalline materials:
--crystallize at melting temp, Tm
--have abrupt change in spec.
vol. at Tm

• Glasses:
--do not crystallize
--spec. vol. varies smoothly with T
Adapted from Fig. 13.5, Callister, 6e.
--Glass transition temp, Tg
• Viscosity:
--relates shear stress & dv
velocity gradient: 
dy
--has units of (Pa-s)

9
 GLASS VISCOSITY VS T AND IMPURITIES
• Viscosity decreases with T increase
• Impurities lower Tdeform

from E.B. Shand, Engineering Glass,

Modern Materials, Vol. 6, Academic
Press, New York, 1968, p. 262.

10
 Important Temperatures
•Melting point = viscosity of 10 Pa.s
•Working point= viscosity of 1000 Pa.s
•Softening point= viscosity of 4x107Pa.s
Temperature above which glass cannot
be handled without altering dimensions)
•Annealing point= viscosity of 1012 Pa.s.
•Strain point = viscosity of 3x1013Pa.s
Fracture occurs before deformation

• Viscosity decreases with T

• Impurities lower Tdeform
 Silicates
– Combine SiO44- tetrahedra by having them
share corners, edges, or faces

Mg2SiO4 Ca2MgSi2O7

– Cations such as Ca2+, Mg2+, & Al3+ act to

neutralize & provide ionic bonding
 Layered Silicates
• Layered silicates (clay
silicates)
– SiO4 tetrahedra connected
together to form 2-D plane

• (Si2O5)2-
• So need cations to balance =
charge
 Layered Silicates
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Adapted from Fig.

12.14, Callister 7e.

Note: these sheets loosely bound by van der Waal’s forces

 Layered Silicates

• Can change the counterions

– this changes layer spacing
– the layers also allow absorption of water
• Micas: KAl3Si3O10(OH)2
• Bentonite
– used to seal wells
– packaged dry
– swells 2-3 fold in H2O
– pump in to seal up well so no polluted ground water seeps
in to contaminate the water supply.
– Used in bonding Foundry Sands and Taconite pellets
 Carbon Forms
• Carbon black – amorphous –
surface area ca. 1000 m2/g
• Diamond
– tetrahedral carbon
• hard – no good slip planes
• brittle – can cleave (cut) it
– large diamonds – jewelry
– small diamonds
• often man made - used for
cutting tools and polishing
– diamond films
• hard surface coat – cutting
tools, medical devices, etc.
 Carbon Forms - Graphite
• layer structure – aromatic layers

– weak van der Waal’s forces between layers

– planes slide easily, good lubricant
 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

Adapted from Figs.

12.18 & 12.19,
Callister 7e.
 Defects in Ceramic Structures
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig. 12.21, Callister
7e. (Fig. 12.21 is from W.G.
Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Frenkel
Defect

QD / kT
• Equilibrium concentration of defects ~e
 Mechanical Properties

We know that ceramics are more brittle

than metals. Why?
• Consider method of deformation
– slippage along slip planes
• in ionic solids this slippage is very difficult
• too much energy needed to move one anion
past another anion (like charges repel)
 Measuring Elastic Modulus
• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing often used.
--tensile tests are difficult for brittle materials!
cross section F Adapted from Fig. 12.32,
L/2 L/2 Callister 7e.
d R
b d = midpoint
rect. circ.
deflection
• Determine elastic modulus according to:
F F L3 F L3
x E= =
F d 4bd 3 d 12 p R4
slope =
d rect. circ.
cross cross
d section section
linear-elastic behavior
 Measuring Strength
• 3-point bend test to measure room T strength.
cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b d = midpoint
rect. circ.
deflection
location of max tension

• Flexural strength: • Typ. values:

Material sfs (MPa) E(GPa)
1.5Ff L Ff L
s fs   Si nitride 250-1000 304
bd 2 pR3 Si carbide 100-820 345
F rect. Al oxide 275-700 393
Ff x glass (soda) 69 69
Data from Table 12.5, Callister 7e.

d
dfs
 Mechanical Issues:
• Properties are significantly dependent on
processing – and as it relates to the level of
Porosity:
• E = E0(1-1.9P+0.9P2) – P is fraction porosity
• sfs = s0e-nP -- s0 & n are empirical values

• Because the very unpredictable nature of

ceramic defects, we do not simply add a factor
of safety for tensile loading
• We may add compressive surface loads
• We often choose to avoid tensile loading at all – most
ceramic loading of any significance is compressive (consider
buildings, dams, brigdes and roads!)
 Application: Refractories
• Need a material to use in high temperature furnaces.
• Consider the Silica (SiO2) - Alumina (Al2O3) system.
• Phase diagram shows:
mullite, alumina, and crystobalite as candidate refractories.

2200 3Al2O3-2SiO2
T(°C)
mullite
2000 Liquid
(L) alumina + L
Adapted from Fig. 12.27,
1800 Callister 7e. (Fig. 12.27
mullite is adapted from F.J. Klug
crystobalite alumina and R.H. Doremus,
+L +L + "Alumina Silica Phase
1600 mullite Diagram in the Mullite
Region", J. American
mullite Ceramic Society 70(10),
+ crystobalite p. 758, 1987.)
1400
0 20 40 60 80 100
Composition (wt% alumina)
 Application: Die Blanks
• Die blanks: die Ad
-- Need wear resistant properties! Ao tensile
force
die
Adapted from Fig. 11.8 (d),
Courtesy Martin Deakins, GE Callister 7e.
Superabrasives, Worthington,
OH. Used with permission.

• Die surface:
-- 4 mm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide Courtesy Martin Deakins, GE
substrate. Superabrasives, Worthington,
OH. Used with permission.
-- polycrystalline diamond helps control
fracture and gives uniform hardness
in all directions.
 Application: Cutting Tools
• Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

• Solutions: oil drill bits blades

-- manufactured single crystal
or polycrystalline diamonds coated single
crystal diamonds
in a metal or resin matrix.
-- optional coatings (e.g., Ti to help
diamonds bond to a Co matrix polycrystalline
diamonds in a resin
via alloying)
matrix.
-- polycrystalline diamonds
Photos courtesy Martin Deakins,
resharpen by microfracturing GE Superabrasives, Worthington,
OH. Used with permission.
along crystalline planes.
 Application: Sensors
• Example: Oxygen sensor ZrO2
• Principle: Make diffusion of ions Ca 2+
fast for rapid response.
• Approach:
Add Ca impurity to ZrO2: A Ca 2+ impurity
-- increases O2- vacancies removes a Zr 4+ and a
-- increases O2- diffusion rate O2- ion.

• Operation:
sensor
-- voltage difference
gas with an reference
produced when unknown, higher gas at fixed
O2- ions diffuse oxygen content O2-
oxygen content
diffusion
from the external
surface of the sensor
to the reference gas. + -
voltage difference produced!
 Alternative Energy – Titania Nano-Tubes
"This is an amazing material architecture for
water photolysis," says Craig Grimes, professor
of electrical engineering and materials science
and engineering. Referring to some recent finds
of his research group (G. K. Mor, K. Shankar,
M. Paulose, O. K. Varghese, C. A. Grimes,
Enhanced Photocleavage of Water Using Titania
Nanotube-Arrays, Nano Letters, vol. 5, pp. 191-
195.2005 ), "Basically we are talking about
taking sunlight and putting water on top of this
material, and the sunlight turns the water into
hydrogen and oxygen. With the highly-ordered
titanium nanotube arrays, under UV
illumination you have a photoconversion
efficiency of 13.1%. Which means, in a nutshell,
you get a lot of hydrogen out of the system per
photon you put in. If we could successfully shift
its bandgap into the visible spectrum we would
have a commercially practical means of
generating hydrogen by solar energy.
 Ceramic Fabrication Methods-I
GLASS PARTICULATE CEMENTATION
FORMING FORMING
• Pressing: plates, dishes, cheap glasses
Pressing
Gob --mold is steel with
operation
graphite lining
Parison
mold • Fiber drawing:
Compressed
• Blowing: air

suspended
Parison

Finishing wind up
mold
Adapted from Fig. 13.8, Callister, 7e. (Fig. 13.8 is adapted from C.J. Phillips,
Glass: The Miracle Maker, Pittman Publishing Ltd., London.)
 Sheet Glass Forming
• Sheet forming – continuous draw
– originally sheet glass was made by “floating”
glass on a pool of mercury – or tin

Adapted from Fig. 13.9, Callister 7e.

Modern Plate/Sheet Glass making:

Image from Prof. JS Colton, Ga. Institute of Technology

 Heat Treating Glass
• Annealing:
--removes internal stress caused by uneven cooling.
• Tempering:
--puts surface of glass part into compression
--suppresses growth of cracks from surface scratches.
--sequence:
before cooling surface cooling further cooled
cooler compression
hot hot tension
cooler compression

--Result: surface crack growth is suppressed.

 Ceramic Fabrication Methods-IIA
GLASS PARTICULATE CEMENTATION
FORMING FORMING
• Milling and screening: desired particle size
• Mixing particles & water: produces a "slip"
• Form a "green" component Ao
container die holder Adapted from
--Hydroplastic forming: force
ram bille extrusion Ad Fig. 11.8 (c),
extrude the slip (e.g., into a pipe) t Callister 7e.
container die
--Slip casting:
pour slip absorb water pour slip drain “green
into mold into mold into mold mold ceramic” Adapted from Fig.
“green 13.12, Callister 7e.
ceramic” (Fig. 13.12 is from
W.D. Kingery,
Introduction to
Ceramics, John
Wiley and Sons,
Inc., 1960.)
solid component hollow component
• Dry and fire the component
 Clay Composition
A mixture of components used

(50%) 1. Clay
(25%) 2. Filler – e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
binds it together

aluminosilicates + K+, Na+, Ca+

 Features of a Slip
Shear
• Clay is inexpensive
• Adding water to clay
-- allows material to shear easily charge
along weak van der Waals bonds neutral
-- enables extrusion
-- enables slip casting

weak van
der Waals
• Structure of bonding
4+
Kaolinite Clay: charge Si
3+
Adapted from Fig. 12.14, Callister 7e. neutral Al
(Fig. 12.14 is adapted from W.E. Hauth, -
"Crystal Chemistry of Ceramics", American
OH
2-
Ceramic Society Bulletin, Vol. 30 (4), 1951, O
p. 140.)

Shear
 Drying and Firing
• Drying: layer size and spacing decrease. Adapted from Fig.
13.13, Callister 7e.
(Fig. 13.13 is from
W.D. Kingery,
Introduction to
Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet slip partially dry “green” ceramic

Drying too fast causes sample to warp or crack due to non-uniform shrinkage
• Firing:
--T raised to (900-1400°C)
--vitrification: liquid glass forms from clay and flows between
SiO2 particles. Flux melts at lower T.
Adapted from Fig. 13.14,
Si02 particle Callister 7e.
(quartz) (Fig. 13.14 is courtesy H.G.
Brinkies, Swinburne
micrograph of glass formed University of Technology,
porcelain around Hawthorn Campus,
the particle Hawthorn, Victoria,
Australia.)

70mm
 Ceramic Fabrication Methods-IIB
GLASS PARTICULATE CEMENTATION
FORMING FORMING
Sintering: useful for both clay and non-clay compositions.
• Procedure:
-- produce ceramic and/or glass particles by grinding
-- place particles in mold
-- press at elevated T to reduce pore size.
• Aluminum oxide powder:
-- sintered at 1700°C
for 6 minutes.
Adapted from Fig. 13.17, Callister 7e.
(Fig. 13.17 is from W.D. Kingery, H.K.
Bowen, and D.R. Uhlmann, Introduction
to Ceramics, 2nd ed., John Wiley and
Sons, Inc., 1976, p. 483.)

15 mm
 Powder Pressing
Sintering - powder touches - forms neck &
gradually neck thickens
– add processing aids to help form neck
– little or no plastic deformation
Uniaxial compression - compacted in single direction
Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope

Hot pressing - pressure + heat Adapted from Fig. 13.16, Callister 7e.
 Tape Casting
• thin sheets of green ceramic cast as flexible tape
• used for integrated circuits and capacitors
• cast from liquid slip (ceramic + organic solvent)

Adapted from Fig. 13.18, Callister 7e.

 Ceramic Fabrication Methods-III
GLASS PARTICULATE CEMENTATION
FORMING FORMING
• Produced in extremely large quantities.
• Portland cement:
-- mix clay and lime bearing materials
-- calcinate (heat to 1400°C)
-- primary constituents:
tri-calcium silicate
di-calcium silicate
• Adding water
-- produces a paste which hardens
-- hardening occurs due to hydration (chemical reactions
with the water).
• Forming: done usually minutes after hydration begins.
 Applications: Advanced Ceramics

Heat Engines • Disadvantages:

– Brittle
• Advantages: – Too easy to have voids-
– Run at higher temperature weaken the engine
– Excellent wear & – Difficult to machine
corrosion resistance
– Low frictional losses
– Ability to operate without
a cooling system
– Low density
• Possible parts – engine block, piston coatings, jet engines
Ex: Si3N4, SiC, & ZrO2
 Applications: Advanced Ceramics

• Ceramic Armor
– Al2O3, B4C, SiC & TiB2
– Extremely hard materials
• shatter the incoming projectile
• energy absorbent material underneath
 Applications: Advanced Ceramics
Electronic Packaging
• Chosen to securely hold microelectronics &
provide heat transfer
• Must match the thermal expansion coefficient of
the microelectronic chip & the electronic
packaging material. Additional requirements
include:
– good heat transfer coefficient
– poor electrical conductivity

• Materials currently used include:

• Boron nitride (BN)
• Silicon Carbide (SiC)
• Aluminum nitride (AlN)
– thermal conductivity 10x that for Alumina
– good expansion match with Si
 Chapter 9: Phase Diagrams
ISSUES TO ADDRESS...
• When we combine two elements...
what is the resulting equilibrium state?
• In particular, if we specify...
-- the composition (e.g., wt% Cu - wt% Ni), and
-- the temperature (T)
then...
How many phases form?
What is the composition of each phase?
What is the amount of each phase?

Phase A Phase B

Nickel atom
Copper atom Chapter 9 - 78
 Phase Equilibria: Solubility Limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

Sugar/Water Phase Diagram

• Solubility Limit: 100
Maximum concentration for Solubility

Temperature (ºC)
which only a single phase 80 Limit L
solution exists. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit for sugar in i.e., syrup) (solid
water at 20ºC? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20ºC, if C < 65 wt% sugar: syrup

Sugar
Water

C = Composition (wt% sugar)

At 20ºC, if C > 65 wt% sugar:
syrup + sugar Chapter 9 - 79
 Components and Phases
• Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that form (e.g., a and b).

Aluminum- b (lighter
Copper
phase)
Alloy

a(darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

Chapter 9 - 80
 Effect of Temperature & Composition
• Altering T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.
B (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
100

80 L
Temperature (ºC)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)
Chapter 9 - 81
 Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally soluble in one another for all proportions.

Chapter 9 - 82
 Phase Diagrams
• Indicate phases as a function of T, C, and P.
• For this course:
- binary systems: just 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
T(ºC)
Phase
1600 • 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 • 3 different phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
1100
(FCC solid Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
solution) Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni Chapter 9 - 83
 Isomorphous Binary Phase Diagram
• Phase diagram: T(ºC)
Cu-Ni system. 1600

• System is: 1500 L (liquid) Cu-Ni

-- binary phase
i.e., 2 components: 1400
diagram
Cu and Ni.
1300
-- isomorphous
i.e., complete 1200 a
solubility of one
component in 1100
(FCC solid
another; a phase solution)
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991).
Chapter 9 - 84
 Phase Diagrams:
Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.
T(ºC)
• Examples: 1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a

B (1250ºC,35)
1500
Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
Adapted from Fig. 9.3(a), Callister &
solution)
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100ºC,60)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991). 1000
0 20 40 60 80 100 wt% Ni
Chapter 9 - 85
 Phase Diagrams:
Determination of phase compositions
• Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190ºC:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250ºC: CL C 0 Ca wt% Ni
Both a and L present Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Ca = C solidus ( = 43 wt% Ni) Park, OH (1991).

Chapter 9 - 86
 Phase Diagrams:
Determination of phase weight fractions
• Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase. Cu-Ni
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43  35
WL 
20 3032 35 40 43 50
  0.73 CL C0 Ca wt% Ni
R +S 43  32
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R
Wa 
Phase Diagrams of Binary Nickel Alloys, P.
= 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).

Chapter 9 - 87
 The Lever Rule
• Tie line – connects the phases in equilibrium with
each other – also sometimes called an isotherm
T(ºC) What fraction of each phase?
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
B
TB ML Ma
a
1200 (solid)
R S

20 30CL R S
C0 40 Ca 50

wt% Ni Ma x S  ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

ML S C  C0 R C  CL
WL    a Wa   0
M L  M a R  S C a  CL R  S C a  CL
 Chapter 9 - 88
 Ex: Cooling of a Cu-Ni Alloy
• Phase diagram: T(ºC) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
system
• Consider 1300 A
L: 35 wt% Ni
microstuctural a: 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a a: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
Chapter 9 - 89
 Cored vs Equilibrium Structures
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

Chapter 9 - 90
 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)
Tensile Strength (MPa)

60

Elongation (%EL)
%EL for pure Cu
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Adapted from Fig. 9.6(b),
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

Chapter 9 - 91
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779ºC L+b b
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE ab
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag)
Chapter 9 - 92
heating
 EX 1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present Pb-Sn
Answer: a + b T(ºC) system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183ºC L+b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
100
W =
a R+S
=
Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - C a Ca C0 Cb
Wb = R = C, wt% Sn
R+S Cb - C a Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 Chapter 9 - 93
99 - 11 88
 EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ a
-- the relative amount 220
200
a R S L+b b
of each phase 183ºC
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
Chapter 9 - 94
 Microstructural Developments
in Eutectic Systems I

• For alloys for which T(ºC)

400
L: C0 wt% Sn

C0 < 2 wt% Sn L
• Result: at room temperature a
300 L
-- polycrystalline with grains of
a phase having L+ a
a
composition C0 200 (Pb-Sn
TE a: C0 wt% Sn
System)

a+ b
100

0 10 20 30
Adapted from Fig. 9.11, C0 C , wt% Sn
Callister & Rethwisch 8e. 2
(room T solubility limit)

Chapter 9 - 95
 Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
• For alloys for which 400
T(ºC)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
at temperatures in a + b range 300 a
L+a
-- polycrystalline with a grains a: C0 wt% Sn
and small b-phase particles 200 a
TE
a
b
100
a+ b Pb-Sn
system
Adapted from Fig. 9.12, 0 10 20 30
Callister & Rethwisch 8e. 2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 - 96
 Microstructural Developments
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.
Micrograph of Pb-Sn
T(ºC) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+a
200
a 183ºC Lb b
TE

100 160 mm
a b b: 97.8 wt% Sn
Adapted from Fig. 9.14,
a: 18.3 wt%Sn Callister & Rethwisch 8e.

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn Chapter 9 - 97
Callister & Rethwisch 8e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

& Rethwisch 8e.

Chapter 9 - 98
 Microstructural Developments
in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and a eutectic microconstituent
• Just above TE :
T(ºC) L: C0 wt% Sn L
a Ca = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
Pb-Sn a S
L+ a Wa = = 0.50
system R+S
a
b b
200 R S L+ WL = (1- Wa) = 0.50
TE S
R
• Just below TE :
100 a+b Ca = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn Chapter 9 - 99
 Hypoeutectic & Hypereutectic
300
L
T(ºC)
L+ a
Adapted from Fig. 9.8,
Callister & Rethwisch 8e. a L+b b
(Fig. 10.8 adapted from
200
TE
(Pb-Sn
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B. a+b System)
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
Handbook, 9th ed.,
Vol. 9,
a b
Metallography and a b
Microstructures, a a b b
American Society for a b
Metals, Materials
Park, OH, 1985.) a b
175 mm 160 mm
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister & Adapted from Fig. 9.14, Callister & Rethwisch 8e.
Rethwisch 8e. Callister & Rethwisch 8e. (Illustration only)
Chapter 9 - 100
 Intermetallic Compounds

Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.

Mg2Pb

Note: intermetallic compound exists as a line on the diagram - not an

area - because of stoichiometry (i.e. composition of a compound
Chapter 9 - 101
is a fixed value).
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool a + b (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other

solid phases
intermetallic compound
S2 S1+S3 - cementite

 cool a + Fe3C (For Fe-C, 727ºC, 0.76 wt% C)

heat

• Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L S2
cool
d +L heat  (For Fe-C, 1493ºC, 0.16 wt% C)

Chapter 9 - 102
 Eutectoid & Peritectic
Peritectic transformation  + L d
Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.
Eutectoid transformation d +
Chapter 9 - 103
 Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(ºC)
1600
points d
- Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C
727ºC = T eutectoid
a
800
B
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 mm
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
a and Fe3C phases a (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,
Chapter 9 - 104
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
 Hypoeutectoid Steel
T(ºC)
1600
d
1400 L
  (Fe-C
  +L
  1200 1148ºC L+Fe3C System)

Fe3C (cementite)
(austenite)
  1000
   + Fe3C Adapted from Figs. 9.24
and 9.29,Callister &
a Rethwisch 8e.
a  800 727ºC (Fig. 9.24 adapted from
 a a Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
Materials Park, OH,
400 1990.)
a 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

pearlite

Hypoeutectoid
100 mm
steel

pearlite proeutectoid ferrite

Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 105
 Hypoeutectoid Steel
T(ºC)
1600
d
1400 L
(Fe-C
a   +L
System)
a  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
 a
1000
 + Fe3C Adapted from Figs. 9.24
Wa = s/(r + s) and 9.29,Callister &
Rethwisch 8e.
800 r s 727ºC
W =(1 - Wa) (Fig. 9.24 adapted from

aRS Binary Alloy Phase

Diagrams, 2nd ed., Vol.
a 600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
pearlite Materials Park, OH,
400 1990.)
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

Wpearlite = W
Wa’ = S/(R + S) 100 mm
Hypoeutectoid
steel
WFe3C =(1 – Wa’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 106
 Hypereutectoid Steel
T(ºC)
1600
d
1400 L (Fe-C
  +L System)
 
 
1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
   +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
Fe3C
 
Rethwisch 8e. (Fig. 9.24
800 adapted from Binary Alloy
  a Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 107
 Hypereutectoid Steel
T(ºC)
1600
d
1400 L (Fe-C
 +L System)
Fe3C 
  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
 +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
W =x/(v + x) Rethwisch 8e. (Fig. 9.24
800 v x adapted from Binary Alloy
WFe3C =(1-W)
a V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
pearlite International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = W
Wa = X/(V + X)
60 mmHypereutectoid
WFe =(1 - Wa) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 108
 Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a
temperature just below the eutectoid,
determine the following:
a) The compositions of Fe3C and ferrite (a).
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite (a) in the 100 g.

Chapter 9 - 109
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Ca = 0.022 wt% C
CFe3C = 6.70 wt% C

b) Using the lever rule with 1600

the tie line shown d
1400 L
R C  Ca T(ºC)
WFe 3C   0   +L
R  S CFe 3C  Ca

Fe C (cementite)
1200 1148ºC L+Fe3C
(austenite)
0.40  0.022
  0.057 1000
 + Fe3C
6.70  0.022
800 727ºC
R S
Amount of Fe3C in 100 g 600 a + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Ca C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 9 - 110
 Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Ca = 0.022 wt% C
Cpearlite = C = 0.76 wt% C
1600
d
1400 L
V C  Ca T(ºC)  +L
Wpearlite   0 

Fe C (cementite)
V  X C  Ca 1200
(austenite)
1148ºC L+Fe3C

0.40  0.022 1000

  0.512  + Fe3C
0.76  0.022
800 727ºC
VX
Amount of pearlite in 100 g 600 a + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Ca C0 C C, wt% C
= (100 g)(0.512) = 51.2 g
Chapter 9 - 111
 VMSE: Interactive Phase Diagrams
Microstructure, phase compositions, and phase fractions respond interactively

Change alloy composition Chapter 9 - 112

 Alloying with Other Elements

• Teutectoid changes: • Ceutectoid changes:

Ceutectoid (wt% C)
Ti
T Eutectoid (ºC)

Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni

wt. % of alloying elements wt. % of alloying elements

Adapted from Fig. 9.34,Callister & Rethwisch 8e. Adapted from Fig. 9.35,Callister & Rethwisch 8e.
(Fig. 9.34 from Edgar C. Bain, Functions of the (Fig. 9.35 from Edgar C. Bain, Functions of the
Alloying Elements in Steel, American Society for Alloying Elements in Steel, American Society for
Metals, 1939, p. 127.) Metals, 1939, p. 127.)

Chapter 9 - 113
 Summary

• Phase diagrams are useful tools to determine:

-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
given the temperature and composition of the system.
• The microstructure of an alloy depends on
-- its composition, and
-- whether or not cooling rate allows for maintenance of
equilibrium.
• Important phase diagram phase transformations include
eutectic, eutectoid, and peritectic.

Chapter 9 - 114
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 9 - 115