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Reminders

Exam II: Wednesday March 25th


Quiz: Wednesday March 18th
Material: Chapters 6 - 10

Chapter 11 - 1

Chapter 11: Applications and


Processing of Metal Alloys
ISSUES TO ADDRESS...
How are commercial alloys classified and what are
their common applications?
What are some of the common fabrication techniques
for metals? How do they alter the properties?
What heat treatment procedures are used to improve the
mechanical properties of both ferrous and nonferrous
alloys?

Chapter 11 - 2

Fig_11-1

Chapter 11 -

How much steel is produced in the US?


A.
B.
C.
D.
E.

5,000 metric tons


100,000 metric tons
1 million metric tons
5 million metric tons
100 million metric tons

Chapter 11 -

Chapter 11 -

americanresources.org

Chapter 11 -

World primary Titanium sponge


production volumes increased by
11% to 222 thousand tons in 2013
compared with production in 2012.
New production capacities are to be
introduced by Ukraine and Canada.
Commercial aerospace industry
supports the market with high
demand for titanium. In Singapore,
on the contrary, a TiO2 plant was
closed in 2013 due to high prices
and sluggish distribution channels.
http://mcgroup.co.uk/researches/titanium

Chapter 11 -

Wide spread use of steel due to:


iron-containing compounds are abundant
in the Earths crust
Relatively economical extraction, refining, alloying
and fabrication
Ferrous alloys are extremely
versatile
Disadvantage: corrosion
density
Sao Francisco Craton, Minas Gerais,
ChapterBrazil
11 - 8

Chapter 11 -

Chapter 11 -

Classification of Metal Alloys


Metal Alloys

Ferrous
Steels
Steels
<1.4wt%C
<1.4
wt% C

Cast Irons
Cast
Irons
3-4.5
wt%C
3-4.5 wt% C

microstructure: ferrite,
graphite/cementite

T(C)
1600

1400
1200

austenite

600
400

0
(Fe)

L+ Fe3C

1148C
4.30

727C

Eutectoid:
0.76

Fig. 9.24, Callister & Rethwisch 9e.

+L

1000

800
ferrite

Adapted from Fig.


11.1, Callister &
Rethwisch 9e.

Nonferrous

Eutectic:

+ Fe3C

Fe3C
cementite

+ Fe3C
3

[Adapted from Binary Alloy Phase


Diagrams, 2nd edition, Vol. 1, T. B.
Massalski (Editor-in-Chief), 1990.
Reprinted by permission of ASM
International, Materials Park, OH.]

Co , wt% C

6.7

Chapter 11 - 11

Steels
High Alloy

Low Alloy
low carbon Med carbon
<0.25 wt% C 0.25-0.6wt% C

high carbon
0.6-1.4wt% C

heat
plain
treatable
Cr,V
Cr, Ni
Additions none
none
none
Mo,Nb
Mo
Example 1010 4310
1040
4340 1095
Hardenability 0
+
+
++
++
TS
0
+
++
+
EL
+
+
0
-

Name

plain

Uses

auto
struc.
sheet

HSLA

bridges
towers
press.
vessels

plain

crank
shafts
bolts
hammers
blades

pistons
gears
wear
applic.

wear
applic.

tool
Cr, V,
Mo, W
4190
+++
++
-drills
saws
dies

increasing strength, cost, decreasing ductility

stainless
Cr, Ni, Mo
304, 409
varies
varies
++
high T
applic.
turbines
furnaces
Very corros.
resistant

Based on data provided in Tables 11.1(b), 13.2(b), 11.3, and 11.4, Callister & Rethwisch 9e.
Chapter 11 - 12

Ferrous Alloys
Iron-based alloys
Steels
Cast Irons
Nomenclature for steels (AISI/SAE)
10xx Plain Carbon Steels
11xx Plain Carbon Steels (resulfurized for machinability)
15xx Mn (1.00 - 1.65%)
40xx Mo (0.20 ~ 0.30%)
43xx Ni (1.65 - 2.00%), Cr (0.40 - 0.90%), Mo (0.20 - 0.30%)
44xx Mo (0.5%)
where xx is wt% C x 100
example: 1060 steel plain carbon steel with 0.60 wt% C
Stainless Steel >11% Cr
Chapter 11 - 13

Ferrous Alloys:
Advanced High Strength Steels (AHSS)

AISI: www.steel.org (2006)

Chapter 11 - 14

Dual Phase Steels


Typical: C: 0.05 - 0.15 Mn: 1.0 2.0
Others: Si, Cr, Ni, Mo, Nb, V
0.15C, 1.5 Mn, 1.5 Si
WQ from 775oC

V 30 %; C 0.17
810 oC
V 9 %; C 0.45
750 oC

A.De et al. Adv. Mat.


Proc. 2003

C = 0.06
Ferrite-martensite
Chapter 11 microstructures

Strengthening in DP Steels

Davies (1978)

Strength increase follows rule of mixtures for


composites: T = Vff + VMM
Chapter 11 - 16

Cast Irons
Ferrous alloys with > 2.14 wt% C
more commonly 3 - 4.5 wt% C
Low melting relatively easy to cast
Generally brittle
Cementite is a metastable compound, it can
decompose to ferrite + graphite
Fe3C 3 Fe () + C (graphite)
generally a slow process

Chapter 11 - 17

Fe-C True Equilibrium Diagram


T(C)
1600

Graphite formation
promoted by

1400

Si > 1 wt%

Austenite

1200

slow cooling

Liquid +
Graphite

+L
1153C
4.2 wt% C

1000

+ Graphite
800
0.65

740C
600

+ Graphite

Fig. 11.2, Callister & Rethwisch 9e.


[Adapted from Binary Alloy Phase
Diagrams, T. B. Massalski (Editor-inChief), 1990. Reprinted by permission of
ASM International, Materials Park, OH.]

400
(Fe)

90

100

C, wt% C

Chapter 11 - 18

Types of Cast Iron


Figs. 11.3(a) & (b),
Gray iron
Callister &
Rethwisch 9e.
[Courtesy of C. H.
graphite flakes
Brady and L. C. Smith,
National Bureau of
Standards, Washington,
gray fracture surface
DC (now the National
Institute of Standards
Technology,
weak & brittle in tension and
Gaithersburg, MD]
stronger in compression
excellent vibrational dampening
wear resistant
Ductile (or Nodular) iron
add Mg and/or Ce
graphite as nodules not flakes
matrix often pearlite or ferrite
Valves, pump bodies,
crankshafts, gears.

Chapter 11 - 19

Production of Cast Irons


Fig.11.5, Callister & Rethwisch 9e.
(Adapted from W. G. Moffatt, G. W.
Pearsall, and J. Wulff, The Structure and
Properties of Materials, Vol. I, Structure, p.
195. Copyright 1964 by John Wiley &
Sons, New York. Reprinted by permission of
John Wiley & Sons, Inc.)

Chapter 11 - 20

Types of Cast Iron (cont.)

< 1 wt% Si
pearlite + cementite
very hard and brittle
Fracture surface:
white appearance

heat treat white iron at 800-900 C


graphite in rosettes within ferrite matrix
reasonably strong and ductile

Reprinted with permission of the


Iron Castings Society, Des Plaines, IL

Malleable iron

Courtesy of Amcast Industrial Corporation

White iron

Figs. 11.3(c) & (d),


Callister &
Rethwisch 9e.

Chapter 11 - 21

Types of Cast Iron (cont.)


graphite nodules and flakes
some Mg or Ce added but less than
used in nodular cast irons
relatively high thermal conductivity
good resistance to thermal shock
lower oxidation at elevated
temperatures
diesel engine blocks

Courtesy of Sinter-Cast, Ltd.

Compacted graphite iron

Fig. 11.3(e), Callister & Rethwisch 9e.

Chapter 11 - 22

Limitations of Ferrous Alloys


1) Relatively high densities
2) Relatively low electrical conductivities
3) Generally poor corrosion resistance

Chapter 11 - 23

Classification scheme for


nonferrous alloys

Fig. 11.6

Chapter 11 - 24

Nonferrous Alloys
Cu Alloys

Al Alloys

-low : 2.7 g/cm3


Brass: Zn is subst. impurity
(costume jewelry, coins)
-Cu, Mg, Si, Mn, Zn additions
Bronze : Sn, Al, Si, Ni are
-solid sol. or precip.
subst. impurities(stronger,
strengthened (struct.
corrosion resistant)
aircraft parts)
Cu-Be :
precip. hardened
Mg Alloys
NonFerrous
for strength
-very low : 1.7 g/cm3
Alloys
(bushings)
- Powder ignites easily
- Steering wheel, laptop

Ti Alloys

Refractory metals
-relatively low : 4.5 g/cm3
-high melting Ts
vs 7.9 for steel
Noble metals -Nb, Mo, W, Ta
-reactive at high Ts -Ag, Au, Pt
-oxid./corr. resistant
- space applic.
Based on discussion and data provided in Section 11.3, Callister & Rethwisch 9e.
Chapter 11 - 25

Temper Designation Scheme for


Aluminum Alloys
Aluminum (Al) alloys are classified as either cast or wrought.
Cast Al alloys: e.g., 295.0, 356.0
Temper designation indicates the mechanical and/or heat treatment the alloy
has been subjected to.

Table. 11.7

Chapter 11 - 26

Metal Fabrication
How do we fabricate metals?
Example: Steelmaking
Extract metal from ore
https://www.youtube.com/watch?v=9l7JqonyoKA

Recycling through scrap remelting


https://www.youtube.com/watch?NR=1&v=T1CJ5NP
W8MU&feature=endscreen

Chapter 11 - 27

Metal Fabrication
How do we fabricate metals?
Blacksmith - hammer (forged)
Cast molten metal into mold

Forming Operations
Rough stock formed to final shape

Hot working

vs.

Deformation temperature
high enough for
recrystallization
Large deformations

Cold working
Deformation below
recrystallization
temperature
Strain hardening occurs
Small deformations
Chapter 11 - 28

Metal Fabrication Methods (i)


FORMING

CASTING

MISCELLANEOUS

Forging (Hammering; Stamping) Rolling (Hot or Cold Rolling)


(wrenches, crankshafts)
force

(I-beams, rails, sheet & plate)


roll

die
A o blank

A d often at

elev. T

Drawing

force

Ao

Ad

roll

Extrusion

(rods, wire, tubing)


die

Ao

(rods, tubing)
Ao
tensile
force

die
die must be well lubricated & clean

Ad

force

container

ram

billet

Adapted from
Fig. 11.9,
Callister &
Rethwisch 9e.

die holder
extrusion

Ad

die
ductile metals, e.g. Cu, Al (hot)
container

Chapter 11 - 29

Metal Fabrication Methods (ii)


FORMING

CASTING

MISCELLANEOUS

Casting- mold is filled with molten metal


metal melted in furnace, perhaps alloying
elements added, then cast in a mold
common and inexpensive
gives good production of shapes
weaker products, internal defects
good option for brittle materials

Chapter 11 - 30

Metal Fabrication Methods (iii)


FORMING

CASTING

MISCELLANEOUS

Sand Casting
(large parts, e.g.,
auto engine blocks)

What material will withstand T >1600C


and is inexpensive and easy to mold?
Answer: sand!!!

Sand

Sand

molten metal

To create mold, pack sand around form


(pattern) of desired shape

Chapter 11 - 31

Metal Fabrication Methods (v)


FORMING

CASTING

Die Casting
-- high volume
-- for alloys having low melting
temperatures

MISCELLANEOUS
Continuous Casting
-- simple shapes
(e.g., rectangular slabs,
cylinders)
molten
solidified

Investment Casting:
https://www.youtube.com/watch?v=BX8w-GUPz1w

Chapter 11 - 32

Metal Fabrication Methods (vi)


FORMING

CASTING

Powder Metallurgy
(metals w/low ductilities)

MISCELLANEOUS

Welding
(when fabrication of one large
part is impractical)

pressure

filler metal (melted)


base metal (melted)
fused base metal

heat

area
contact
densify

unaffected
piece 1

heat-affected zone
unaffected
Fig. 11.10, Callister
piece 2
& Rethwisch 9e.

Heat-affected zone:
point contact
at low T

densification
by diffusion at
higher T

(region in which the


microstructure has been
changed).

[From Iron Castings


Handbook, C.F. Walton
and T.J. Opar (Ed.),
Iron Castings Society,
Des Plaines, IL,1981.]

Chapter 11 - 33

Thermal Processing of Metals

Heat treating following prior processing affects final properties.


Effect of prior processing can be canceled out.
Thermal processing to soften (e.g. full anneal) or strengthen
material (e.g. precipitation strengthening).

Chapter 11 - 34

Thermal Processing of Metals


Annealing: Heat to Tanneal, then cool slowly.
Stress Relief: Reduce

Spheroidize (steels):

stresses resulting from:


- plastic deformation
- nonuniform cooling
- phase transform.

Make very soft steels for


good machining. Heat just
below Teutectoid & hold for
15-25 h.

Types of
Annealing

Full Anneal (steels):


Make soft steels for
good forming. Heat
to get , then furnace-cool
to obtain coarse pearlite.

Normalize (steels): Deform


steel with large grains. Then heat
treat to allow recrystallization
and formation of smaller grains.
Based on discussion in Section 11.7, Callister & Rethwisch 9e.
Chapter 11 - 35

Heat Treatment Temperature-Time Paths


a) Full Annealing

b) Quenching
c) Tempering
(Tempered
Martensite)

Fig. 10.25, Callister & Rethwisch 9e.


[Adapted from H. Boyer (Editor), Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, 1977.
Reproduced by permission of ASM
International, Materials Park, OH.]

b)

a)
c)
Chapter 11 - 36

Hardenability -- Steels
Hardenability measure of the ability to form martensite
Jominy end quench test used to measure hardenability.

specimen
(heated to
phase field)
24C water

flat ground
Rockwell C
hardness tests

Fig. 11.12, Callister &


Rethwisch 9e.
(Adapted from A.G. Guy,
Essentials of Materials Science,
McGraw-Hill Book Company,
New York, 1978.)

https://www.youtube.com/watch?v=nEV6RqDr9CA

Chapter 11 - 37

Hardenability -- Steels
Hardenability measure of the ability to form martensite
Jominy end quench test used to measure hardenability.

specimen
(heated to
phase field)
24C water

flat ground
Rockwell C
hardness tests

Fig. 11.12, Callister &


Rethwisch 9e.
(Adapted from A.G. Guy,
Essentials of Materials Science,
McGraw-Hill Book Company,
New York, 1978.)

Hardness, HRC

Plot hardness versus distance from the quenched end.

Fig. 11.13, Callister &


Rethwisch 9e.

Distance from quenched end


Chapter 11 - 38

Reason Why Hardness Changes with


Distance
Hardness, HRC

The cooling rate decreases with distance from quenched end.


60
40
20

distance from quenched end (in)

T(C)

0%
100%

600

Fig. 11.14, Callister & Rethwisch 9e.


[Adapted from H. Boyer (Ed.), Atlas of
Isothermal Transformation and Cooling
Transformation Diagrams, 1977. Reproduced
by permission of ASM International, Materials
Park, OH.]

400
200

M(start)
AM

0 M(finish)

0.1

10

100

1000

Time (s)
Chapter 11 - 39

Hardenability vs Alloy Composition


100

(Adapted from figure furnished courtesy


Republic Steel Corporation.)

"Alloy Steels"

2 Cooling rate (C/s)


100

4340

80 %M
50

40

Fig. 11.15, Callister & Rethwisch 9e.

10

60

Hardness, HRC

Hardenability curves for


five alloys each with,
C = 0.4 wt% C

4140
8640

20

5140

0 10 20 30 40 50
Distance from quenched end (mm)

800

TE
T(C)
(4140, 4340, 5140, 8640)
600
-- contain Ni, Cr, Mo
A
B
(0.2 to 2 wt%)
400
-- these elements shift
M(start)
the "nose" to longer times
200
M(90%)
(from A to B)
0 -1
-- martensite is easier
10
10 103 105 Time (s)
to form

Chapter 11 - 40

Precipitation Strengthening
Internal wing structure on Boeing 767
Adapted from chapteropening photograph,
Chapter 11, Callister &
Rethwisch 3e. (courtesy of
G.H. Narayanan and A.G.
Miller, Boeing Commercial
Airplane Company.)

Aluminum is strengthened with precipitates formed


by alloying.
Adapted from Fig. 11.26,
Callister & Rethwisch 8e.
(Fig. 11.26 is courtesy of
G.H. Narayanan and A.G.
Miller, Boeing Commercial
Airplane Company.)

1.5m

Precipitates are developed by heat treating.


Chapter 11 - 42

Precipitation Hardening
Particles impede dislocation motion.
700
Ex: Al-Cu system
T(C)
Procedure:
600
+L
-- Pt A: solution heat treat
(get solid solution)
-- Pt B: quench to room temp.
(retain solid solution)
-- Pt C: reheat to nucleate
small particles within
phase.

500
400

Adapted from Fig.


11.23, Callister &
Rethwisch 9e.

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300
0 B 10

(Al)

Other alloys that precipitation


harden: Temp.
Cu-Be
Cu-Sn
Mg-Al

L
+L

+
20

30

40

CuAl2

50

wt% Cu

composition range
available for precipitation hardening

Pt A (soln heat treat)

Fig. 11.25, Callister & Rethwisch 9e.


(Adapted from J.L. Murray, International
Metals Review 30, p.5, 1985. Reprinted by
permission of ASM International.)

Pt C (precipitate )

Pt B

Time
Chapter 11 - 43

Influence of Precipitation Heat


Treatment on TS, %EL
2014 Al Alloy:
Minima on %EL curves.

30
400
%EL

tensile strength (MPa)

Maxima on TS curves.
Increasing T accelerates
process.

300
200
100

149C

20
10
204C

204C
1min
1h 1day 1mo 1yr
precipitation heat treat time

149C

1min
1h 1day 1mo 1yr
precipitation heat treat time

Fig. 11.28, Callister & Rethwisch 9e. [Adapted from Metals Handbook: Properties and Selection: Nonferrous Alloys
and Pure Metals, Vol. 2, 9th ed., H. Baker (Managing Ed.), 1979. Reproduced by permission of ASM International,
Materials Park, OH.]

Chapter 11 - 44

Summary
Ferrous alloys: steels and cast irons
Non-ferrous alloys:
-- Cu, Al, Ti, and Mg alloys; refractory alloys; and noble metals.
Metal fabrication techniques:
-- forming, casting, miscellaneous.
Hardenability of metals
-- measure of ability of a steel to be heat treated.
-- increases with alloy content.
Precipitation hardening
--hardening, strengthening due to formation of
precipitate particles.
--Al, Mg alloys precipitation hardenable.

Chapter 11 - 45

Chapter 12: Structures & Properties of


Ceramics
ISSUES TO ADDRESS...
How do the crystal structures of ceramic materials
differ from those for metals?
How do point defects in ceramics differ from those
defects found in metals?
How are impurities accommodated in the ceramic lattice?
In what ways are ceramic phase diagrams different from
phase diagrams for metals?
How are the mechanical properties of ceramics
measured, and how do they differ from those for metals?

Chapter 12 - 1

Atomic Bonding in Ceramics


Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.

Degree of ionic character may be large or small:


CaF2: large
SiC: small

Chapter 12 - 2

Factors that Determine Crystal Structure


1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

unstable
2. Maintenance of
Charge Neutrality :

stable

--Net charge in ceramic


should be zero.
--Reflected in chemical
formula:

CaF 2 :

Adapted from Fig. 12.1,


Callister & Rethwisch 9e.

+
-

stable
Ca 2+ +
cation

Fanions
F-

A m Xp
m, p values to achieve
charge neutrality

Chapter 12 - 3

Coordination Number and Ionic Radii

r cation
Coordination Number increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation
r anion
< 0.155

Coord.
Number
linear
2
triangular

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

Adapted from Table 12.2,


Callister & Rethwisch 9e.

cubic

ZnS
(zinc blende)
Adapted from Fig. 12.4,
Callister & Rethwisch 9e.

NaCl
(sodium
chloride)

Adapted from Fig. 12.2,


Callister & Rethwisch 9e.

CsCl
(cesium
chloride)
Adapted from Fig. 12.3,
Callister & Rethwisch 9e.
Chapter 12 - 4

Computation of Minimum Cation-Anion


Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)

a = 2ranion

Chapter 12 - 5

Example Problem: Predicting the Crystal


Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm)
Al 3+
0.053
Fe 2+
0.077
Fe 3+
0.069
Ca 2+
0.100
Anion
O2Cl F-

Answer:

rcation 0.077
=
ranion 0.140
= 0.550
based on this ratio,
-- coord # = 6 because

0.140
0.181
0.133

0.414 < 0.550 < 0.732


-- crystal structure is NaCl
Data from Table 12.3,
Callister & Rethwisch 8e.
Chapter 12 - 6

Rock Salt Structure


Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
cations (Na+) prefer octahedral sites

Adapted from Fig. 12.2,


Callister & Rethwisch 8e.

Chapter 12 - 7

MgO and FeO


MgO and FeO also have the NaCl structure
O2-

rO = 0.140 nm

Mg2+

rMg = 0.072 nm

rMg/rO = 0.514
cations prefer octahedral sites
Adapted from Fig. 12.2,
Callister & Rethwisch 9e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms


Chapter 12 - 8

AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:

Since 0.732 < 0.939 < 1.0,


cubic sites preferred
Fig. 12.3, Callister & Rethwisch 9e.

So each Cs+ has 8 neighbor Cl-

Chapter 12 - 9

ABX3 Crystal Structures


Perovskite structure
Ex: complex oxide
BaTiO3

Adapted from Fig. 12.6,


Callister & Rethwisch 8e.

Chapter 12 - 10

Silicate Ceramics
Most common elements on earth are Si & O

Si4+
O2-

Figs. 12.9 & 12.10, Callister &


Rethwisch 9e

crystobalite

SiO2 (silica) polymorphic forms are quartz,


crystobalite, & tridymite
The strong Si-O bonds lead to a high melting
temperature (1710C) for this material
Chapter 12 - 11

Polymorphic Forms of Carbon


Diamond
tetrahedral bonding of
carbon
hardest material known
very high thermal
conductivity

small crystals used to


grind/cut other materials
diamond thin films
hard surface coatings
used for cutting tools,
medical devices, etc.

Fig. 12.16, Callister &


Rethwisch 9e.

Chapter 12 - 12

Polymorphic Forms of Carbon (cont)


Graphite
layered structure parallel hexagonal arrays of
carbon atoms

Fig. 12.17, Callister


& Rethwisch 9e.

weak forces between layers


planes slide easily over one another -- good
lubricant
Chapter 12 - 13

Polymorphic Forms of Carbon (cont)


Fullerenes and Nanotubes
Fullerenes spherical cluster of 60 carbon atoms, C60
Like a soccer ball
Carbon nanotubes sheet of graphite rolled into a tube
Ends capped with fullerene hemispheres

Adapted from Figs.


12.18 & 12.19, Callister
& Rethwisch 8e.

Chapter 12 - 14

Factors that Determine Crystal Structure


1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

unstable
2. Maintenance of
Charge Neutrality :
--Net charge in ceramic
should be zero.

r cation determines
r anion crystal
structure

Adapted from Fig. 12.1,


Callister & Rethwisch 9e.

stable

stable

CaF 2 :

Ca 2+ +
cation

Fanions
F-

A m Xp
m, p values to achieve
charge neutrality

Chapter 12 - 15

Point Defects in Ceramics (i)


Vacancies
-- vacancies exist in ceramics for both cations and anions
Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy
Fig. 12.18, Callister & Rethwisch 9e.
(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, p.78. Copyright
1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley and
Sons, Inc.)

Anion
Vacancy

Chapter 12 - 16

Point Defects in Ceramics (ii)


Frenkel Defect
-- a cation vacancy-cation interstitial pair.
Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect:

Fig. 12.19, Callister & Rethwisch 9e.


(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, p.78. Copyright
1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley and
Sons, Inc.)

Frenkel
Defect

Equilibrium concentration of defects

Chapter 12 - 17

Ceramic Phase Diagrams


MgO-Al2O3 diagram:
Fig. 12.23, Callister &
Rethwisch 9e.

[Adapted from B. Hallstedt,


Thermodynamic Assessment
of the System MgOAl2O3, J.
Am. Ceram. Soc., 75[6], 1502
(1992). Reprinted by
permission of the American
Ceramic Society.]

Chapter 12 - 18

Mechanical Properties
Ceramic materials are more brittle than metals.
Why is this so?
Consider mechanism of deformation
In crystalline, by dislocation motion
In highly ionic solids, dislocation motion is difficult
few slip systems
resistance to motion of ions of like charge (e.g., anions)
past one another

bend test to measure room-T flexural strength.


cross section

d
b

rect.

L/2

L/2

R
= midpoint
deflection

circ.
location of max tension

Chapter 12 - 19

SUMMARY
Interatomic bonding in ceramics is ionic and/or covalent.
Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.
Imperfections
-- Atomic point: vacancy, interstitial (cation), Frenkel, Schottky
-- Impurities: substitutional, interstitial
-- Maintenance of charge neutrality
Room-temperature mechanical behavior flexural tests

Chapter 12 - 20

Chapter 13: Applications and


Processing of Ceramics
ISSUES TO ADDRESS...
How do we classify ceramics?

What are some applications of ceramics?


How is processing of ceramics different than for metals?

Chapter 13 - 1

Classification of Ceramics
Ceramic Materials
Glasses

Clay Refractories
products

Abrasives Cements

Advanced
ceramics

-optical
-whiteware -bricks for -sandpaper -composites -engine
-composite -structural high T
-cutting
-structural
rotors
(furnaces) -polishing
reinforce
valves
-containers/
bearings
Adapted from Fig. 13.1 and discussion in
-sensors
household
Section 13.2-8, Callister & Rethwisch 8e.

Chapter 13 - 2

Ceramics Application: Die Blanks


Die blanks:
-- Need wear resistant properties!

Die surface:

-- 4 mm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear.

die
Ao
die

Ad

tensile
force

Adapted from Fig. 11.8(d),


Callister & Rethwisch 8e.

Courtesy Martin Deakins, GE


Superabrasives, Worthington,
OH. Used with permission.
Chapter 13 - 3

Ceramics Application:
Cutting Tools
Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

Materials:
-- manufactured single crystal
or polycrystalline diamonds
in a metal or resin matrix.
-- polycrystalline diamonds
resharpen by microfracturing
along cleavage planes.

oil drill bits

blades
Single crystal
diamonds
polycrystalline
diamonds in a resin
matrix.

Photos courtesy Martin Deakins,


GE Superabrasives, Worthington,
OH. Used with permission.
Chapter 13 - 4

Refractories
Materials to be used at high temperatures (e.g., in
high temperature furnaces).
Consider the Silica (SiO2) - Alumina (Al2O3) system.
Silica refractories - silica rich - small additions of alumina
depress melting temperature (phase diagram):
2200
T(C)
2000

3Al2O3-2SiO2
Liquid
(L)

1800

mullite
alumina + L
mullite
+L

crystobalite
+L

1600
1400
0

mullite
+ crystobalite

20

alumina
+
mullite

40
60
80
100
Composition (wt% alumina)

Fig. 12.27, Callister &


Rethwisch 8e. (Fig. 12.27
adapted from F.J. Klug and
R.H. Doremus, J. Am. Cer.
Soc. 70(10), p. 758, 1987.)

Chapter 13 - 5

Advanced Ceramics:
Materials for Automobile Engines
Advantages:
Operate at high
temperatures high
efficiencies
Low frictional losses
Operate without a cooling
system
Lower weights than
current engines

Disadvantages:
Ceramic materials are
brittle
Difficult to remove internal
voids (that weaken
structures)
Ceramic parts are difficult
to form and machine

Potential candidate materials: Si3N4, SiC, & ZrO2


Possible engine parts: engine block & piston coatings
Chapter 13 - 6

Advanced Ceramics:
Materials for Ceramic Armor
Components:
-- Outer facing plates
-- Backing sheet

Properties/Materials:
-- Facing plates -- hard and brittle
fracture high-velocity projectile
Al2O3, B4C, SiC, TiB2
-- Backing sheets -- soft and ductile
deform and absorb remaining energy
aluminum, synthetic fiber laminates

Chapter 13 - 7

Ceramic Fabrication Methods (i)


PARTICULATE
CEMENTATION
GLASS
FORMING
FORMING
Blowing of Glass Bottles:
Pressing: plates, cheap glasses
Gob

Pressing
operation

Parison
mold

-- glass formed by application of


pressure
-- mold is steel with graphite
lining

Fiber drawing:
Compressed
air
Suspended
parison
Finishing
mold
Adapted from Fig. 13.8, Callister & Rethwisch 8e. (Fig. 13.8 is adapted from C.J.
Phillips, Glass: The Miracle Maker, Pittman Publishing Ltd., London.)

wind up
Chapter 13 - 8

Sheet Glass Forming


Sheet forming continuous casting
sheets are formed by floating the molten glass on a pool of
molten tin

Adapted from Fig. 13.9,


Callister & Rethwisch 8e.
Chapter 13 - 9

Glass Structure
Basic Unit:
4Si0 4 tetrahedron
Si 4+
O2-

Quartz is crystalline
SiO2:

Glass is noncrystalline (amorphous)


Fused silica is SiO2 to which no
impurities have been added
Other common glasses contain
impurity ions such as Na+, Ca2+,
Al3+, and B3+
Na +
Si 4+
O2-

(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 8e.
Chapter 13 - 10

Glass Properties
Specific volume (1/r) vs Temperature (T):
Crystalline materials:
Specific volume
Liquid
(disordered)

Supercooled
Liquid

Glasses:

Glass
(amorphous solid)
Crystalline
(i.e., ordered)

Tg

-- crystallize at melting temp, Tm


-- have abrupt change in spec.
vol. at Tm

Tm

Adapted from Fig. 13.6,


Callister & Rethwisch 8e.

solid

-- do not crystallize
-- change in slope in spec. vol. curve at
glass transition temperature, Tg
-- transparent - no grain boundaries to
scatter light

Chapter 13 - 11

Production Processes
Glass windows:
https://www.youtube.com/watch?v=dw7623hu7wM
Glass bottles:
https://www.youtube.com/watch?v=yvqLtTUlZcA

Chapter 13 - 12

Ceramic Fabrication Methods (iia)


GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Hydroplastic forming:
Mill (grind) and screen constituents: desired particle size
Extrude this mass (e.g., into a brick)
Ao
force

container

ram

billet

container

die holder
extrusion

die

Ad

Adapted from
Fig. 12.8(c),
Callister &
Rethwisch 8e.

Dry and fire the formed piece


Chapter 13 - 14

Ceramic Fabrication Methods (iia)


GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Slip casting:
Mill (grind) and screen constituents: desired particle size
Mix with water and other constituents to form slip
Slip casting operation
pour slip
into mold

absorb water
into mold
green
ceramic

solid component

pour slip
into mold

drain
mold

green
ceramic

Adapted from Fig.


13.12, Callister &
Rethwisch 8e. (Fig.
13.12 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

hollow component

Dry and fire the cast piece

Chapter 13 - 15

Porcelain
Porcelain Production:
https://www.youtube.com/watch?v=9lD999ZjD7E

Typical Porcelain Composition


(50%) 1. Clay
(25%) 2. Filler e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass
Chapter 13 - 16

Drying and Firing


Drying: as water is removed - interparticle spacings decrease
shrinkage .
Adapted from Fig.
13.13, Callister &
Rethwisch 8e. (Fig.
13.13 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet body

partially dry

completely dry

Firing:
-- heat treatment between
900-1400C
-- vitrification: liquid glass forms
from clay and flux flows
between SiO2 particles. (Flux
lowers melting temperature).

micrograph of porcelain

Drying too fast causes sample to warp or crack due to non-uniform shrinkage
Si02 particle
(quartz)
glass formed
around
the particle

70mm
Adapted from Fig. 13.14, Callister & Rethwisch 8e.
(Fig. 13.14 is courtesy H.G. Brinkies, Swinburne
University of Technology, Hawthorn Campus,
Hawthorn, Victoria, Australia.)
Chapter 13 - 17

Ceramic Fabrication Methods (iib)


GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Powder Pressing: used for both clay and non-clay compositions.


Powder (plus binder) compacted by pressure in a mold
-- Uniaxial compression - compacted in single direction
-- Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope
-- Hot pressing - pressure + heat

Chapter 13 - 18

Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size

Adapted from Fig. 13.16,


Callister & Rethwisch 8e.

Aluminum oxide powder:


-- sintered at 1700C
for 6 minutes.

Adapted from Fig. 13.17, Callister


& Rethwisch 8e. (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

Chapter 13 - 19

Tape Casting
Thin sheets of green ceramic cast as flexible tape
Used for integrated circuits and capacitors
Slip = suspended ceramic particles + organic liquid
(contains binders, plasticizers)
Fig. 13.18, Callister &
Rethwisch 8e.

Chapter 13 - 20

Ceramic Fabrication Methods (iii)


GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Hardening of a paste paste formed by mixing cement


material with water
Formation of rigid structures having varied and complex
shapes
Hardening process hydration (complex chemical
reactions involving water and cement particles)
Portland cement production of:
-- mix clay and lime-bearing minerals
-- calcine (heat to 1400C)
-- grind into fine powder
https://www.youtube.com/watch?v=m8U76Bm8kDY

Chapter 13 - 21

Summary
Categories of ceramics:
-- glasses
-- clay products
-- refractories
-- cements
-- advanced ceramics

Ceramic Fabrication techniques:


-- glass forming (pressing, blowing, fiber drawing).
-- particulate forming (hydroplastic forming, slip casting,
powder pressing, tape casting)
-- cementation

Heat treating procedures


-- glassesannealing
-- particulate formed piecesdrying, firing (sintering)

Chapter 13 - 22

Homework IV Assignment
11.2, 11.7 (composition only), 11.19,
11.24, 11.D14
Due: Wednesday April 8th, 2015

Homework V Assignment
12.4, 12.5, 13.8, 13.21
Due: Wednesday April 15th, 2015

Exam III: Wednesday April 22nd, 2015


Chapter 14 - 1

Coordination Number and Ionic


Radii
r cation

Coordination Number increases with r


anion
To form a stable structure, how many anions can
surround around a cation?
r cation
r anion
< 0.155

Coord.
Number
linear
2
triangular

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

Adapted from Table 12.2,


Callister & Rethwisch 9e.

cubic

ZnS
(zinc blende)
Adapted from Fig. 12.4,
Callister & Rethwisch 9e.

NaCl
(sodium
chloride)

Adapted from Fig. 12.2,


Callister & Rethwisch 9e.

CsCl
(cesium
chloride)
Adapted from Fig. 12.3,
Callister & Rethwisch 9e.
Chapter 14 - 2

Chapter 14:
Polymer Structures
ISSUES TO ADDRESS...
What are the general structural and chemical
characteristics of polymer molecules?
What are some of the common polymeric
materials, and how do they differ chemically?
How is the structure of polymers different
than that in metals and ceramics ?

Chapter 14 - 3

What is a Polymer?
Poly
many

mer
repeat unit

repeat
unit

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Poly(vinyl chloride) (PVC)

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Adapted from Fig. 14.2, Callister & Rethwisch 9e.

Chapter 14 - 4

Natural Polymers
Originally natural polymers were used
Wood
Rubber
Cotton
Wool
Leather
Silk
Oldest known uses
Rubber balls used by Incas
Biblical reference to pitch
(a natural polymer)
Chapter 14 - 5

Polymer Composition
Most polymers are hydrocarbons
i.e., made up of H and C
Saturated hydrocarbons
Each carbon singly bonded to four other atoms
Example:
Ethane, C2H6
H

H
C

H
C
H

Chapter 14 - 6

Chapter 14 - 7

Unsaturated Hydrocarbons
Double & triple bonds somewhat unstable
can form new bonds
Double bond found in ethylene - C2H4

H
C C

Triple bond found in acetylene - C2H2

H C C H
Chapter 14 - 8

Chemistry and Structure of


Polyethylene
Adapted from Fig.
14.1, Callister &
Rethwisch 9e.

Note: polyethylene is a long-chain hydrocarbon


- paraffin wax for candles is short polyethylene
Chapter 14 - 9

Isomerism
Isomerism
two compounds with same chemical formula can
have quite different structures
for example: C8H18
normal-octane
H H H H H H H H
H C C C C C C C C H

= H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H H H H H H H H

H3C ( CH2 ) CH3


6

2,4-dimethylhexane
CH3
H3C CH CH2 CH CH3
CH2
CH3
Chapter 14 - 10

Bulk or Commodity Polymers

Chapter 14 - 12

Molecular Structures for Polymers

secondary

bonding

Linear

Branched

Cross-Linked

Network

Adapted from Fig. 14.7, Callister & Rethwisch 9e.

Chapter 14 - 15

Polymers Molecular Shape


Molecular Shape chain bending and twisting
are possible by rotation of carbon atoms
around their chain bonds
note: not necessary to break chain bonds
to alter molecular shape
Adapted from Fig.
14.5, Callister &
Rethwisch 9e.

Chapter 14 - 16

Chain End-to-End Distance, r

Fig. 14.6, Callister &


Rethwisch 9e.

Chapter 14 - 17

Polymer Crystallinity
Crystalline regions
thin platelets with chain folds at faces
Chain folded structure
Fig. 14.12, Callister
& Rethwisch 9e.

10 nm

Chapter 14 - 18

Crystallinity in Polymers
Fig. 14.10, Callister
& Rethwisch 9e.

Ordered atomic
arrangements involving
molecular chains
Crystal structures in terms
of unit cells
Example shown
polyethylene unit cell

Chapter 14 - 19

Polymer Crystallinity (cont.)


Polymers rarely 100% crystalline
Difficult for all regions of all chains to
become aligned
crystalline
region

Degree of crystallinity

expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.

amorphous
region

Fig. 14.11, Callister 6e. (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 14 - 20

Semicrystalline Polymers

Spherulite
surface

Some semicrystalline
polymers form
spherulite structures
Alternating chain-folded
crystallites and
amorphous regions
Spherulite structure for
relatively rapid growth
rates

Fig. 14.13, Callister & Rethwisch 9e.

Chapter 14 - 21

MOLECULAR WEIGHT
Molecular weight, M: Mass of a mole of chains.

Low M

high M

Not all chains in a polymer are of the same length


i.e., there is a distribution of molecular weights

Chapter 14 - 22

MOLECULAR WEIGHT DISTRIBUTION


= numerical average

Fig. 14.4, Callister & Rethwisch 9e.

Chapter 14 - 23

Degree of Polymerization, DP
DP = average number of repeat units per chain
H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H

DP = 6

H H H H H H H H H H H H

Chain fraction

mol. wt of repeat unit i


Chapter 14 - 28

Copolymers
two or more monomers
polymerized together
random A and B randomly
positioned along chain
alternating A and B
alternate in polymer chain
block large blocks of A
units alternate with large
blocks of B units
graft chains of B units
grafted onto A backbone
A

Fig. 14.9, Callister &


Rethwisch 9e.

random

alternating

block

graft
Chapter 14 - 29

Chapter 15:
Characteristics, Applications &
Processing of Polymers
ISSUES TO ADDRESS...
What are the tensile properties of polymers and how
are they affected by basic microstructural features?
Hardening, anisotropy, and annealing in polymers.
How does the elevated temperature mechanical
response of polymers compare to ceramics and metals?
What are the primary polymer processing methods?

Chapter 15 - 1

Mechanical Properties of Polymers


Stress-Strain Behavior
brittle polymer

plastic
elastomer
elastic moduli
less than for metals

Adapted from Fig. 15.1,


Callister & Rethwisch 9e.

Fracture strengths of polymers ~ 10% of those for metals


Deformation strains for polymers > 1000%
for most metals, deformation strains < 10%
Chapter 15 - 2

Mechanical Properties of Polymers


Stress-Strain Behavior

www.packaging-gateway.com

Chapter 15 - 3

Mechanisms of DeformationBrittle
Crosslinked and Network Polymers
Initial

Near
Failure

(MPa)
x brittle failure

x plastic failure

aligned, crosslinked
polymer
network polymer

e
Stress-strain curves adapted from Fig. 15.1,
Callister & Rethwisch 9e.

Chapter 15 - 4

Mechanisms of Deformation
Semicrystalline (Plastic) Polymers
(MPa)
Stress-strain curves adapted
from Fig. 15.1, Callister &
Rethwisch 9e. Inset figures
along plastic response curve
adapted from Figs. 15.12 &
15.13, Callister & Rethwisch
9e. (From SCHULTZ, POLYMER
MATERIALS SCIENCE, 1st Edition,
1974. Reprinted by permission of
Pearson Education, Inc., Upper
Saddle River, NJ.)1974, pp 500-501.)

fibrillar
structure

x brittle failure
onset of
necking

plastic failure

near
failure

x
unload/reload

e
crystalline
block segments
separate
undeformed
structure

amorphous
regions
elongate

crystalline
regions align
Chapter 15 - 5

Predeformation by Drawing
Drawing(ex: monofilament fishline)
-- stretches the polymer prior to use
-- aligns chains in the stretching direction
Results of drawing:
-- increases the elastic modulus (E) in the
stretching direction
-- increases the tensile strength (TS) in the
stretching direction
Adapted from Fig. 15.13, Callister &
Rethwisch 9e.
-- decreases ductility (%EL)
(From Schultz, Polymer Materials Science,
1st Edition, 1974. Reprinted by permission
Annealing after drawing...
of Pearson Education, Inc., Upper Saddle
River, NJ.)1974, pp 500-501.)
-- decreases chain alignment
-- reverses effects of drawing (reduces E and
TS, enhances %EL)

Contrast to effects of cold working in metals!


Chapter 15 - 6

Mechanisms of Deformation
Elastomers
(MPa)

x brittle failure

plastic failure

elastomer

e
initial: amorphous chains are
kinked, cross-linked.

Stress-strain curves
adapted from Fig. 15.1,
Callister & Rethwisch 9e.
Inset figures along
elastomer curve (green)
adapted from Fig. 15.15,
Callister & Rethwisch 9e.

final: chains
are straighter,
still
cross-linked

(Fig. 15.15 adapted from Z. D.


Jastrzebski, The Nature and
Properties of Engineering
Materials, 3rd edition.
Copyright 1987 by John
Wiley & Sons, New York.
Reprinted by permission of
John Wiley & Sons, Inc.)

deformation
is reversible (elastic)!

Compare elastic behavior of elastomers with the:


-- brittle behavior (of aligned, crosslinked & network polymers), and
-- plastic behavior (of semicrystalline polymers)
(as shown on previous slides)

Chapter 15 - 7

Thermoplastics vs. Thermosets


Thermoplastics:
-- little crosslinking
-- ductile
-- soften w/heating
-- polyethylene, polypropylene
polycarbonate, polystyrene

Chapter 15 - 8

Thermoplastics vs. Thermosets


Thermosets:
-- significant crosslinking
(10 to 50% of repeat units)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin

Chapter 15 - 9

Influence of T and Strain Rate on Thermoplastics


Decreasing T...
-- increases E
-- increases TS
-- decreases %EL

Increasing
strain rate...
-- same effects
as decreasing T.

(MPa)
80 4C
60

20C

40

Plots for
semicrystalline
PMMA (Plexiglas)

40C

20
0

60C
0

0.1

0.2

to 1.3
0.3

Adapted from Fig. 15.3, Callister & Rethwisch 9e. (Reprinted with permission
from T. S. Carswell and H. K. Nason, Effect of Environmental Conditions on the
Mechanical Properties of Organic Plastics, in Symposium on Plastics. Copyright ASTM
International, 100 Barr Harbor Drive, West Conshohocken, PA 19428.)

Chapter 15 - 10

Melting & Glass Transition Temps.


What factors affect Tm and Tg?

Both Tm and Tg increase with


increasing chain stiffness
Chain stiffness increased by
presence of
1. Bulky sidegroups
2. Chain double bonds

Representative Tg values (C):


PE (low density)
PE (high density)
PVC
PS
PC

- 110
- 90
+ 87
+100
+150

Selected values from


Table 15.2, Callister
& Rethwisch 9e.
Adapted from Fig. 15.18,
Callister & Rethwisch 9e.
Chapter 15 - 11

Time-Dependent Deformation
Stress relaxation test:
-- strain in tension to e
and hold.
-- observe decrease in
stress with time.
tensile test

eo

There is a large decrease in Er


for T > Tg.
5

10
Er (10 s) 3
in MPa 10

rigid solid
(small relax)
transition
region

10

10-1

strain
(t)

viscous liquid

10-3 (large relax)

(amorphous
polystyrene)
Fig. 15.7, Callister &
Rethwisch 9e.
(From A. V. Tobolsky,
Properties and Structures
of Polymers. Copyright
1960 by John Wiley &
Sons, New York.
Reprinted by permission
of John Wiley & Sons,
Inc.)

60 100 140 180 T(C)


Tg

time

Relaxation modulus:

Chapter 15 - 12

Polymer Formation
There are two types of polymerization
Addition (or chain) polymerization
Condensation (step) polymerization
(beyond scope)

Chapter 15 - 13

Addition (Chain) Polymerization


Initiation
R: initiator or catalyst
Propagation

Termination

Chapter 15 - 14

Polymer Additives
Improve mechanical properties, processability,
durability, etc.
Fillers
Added to improve tensile strength & abrasion
resistance, toughness & decrease cost
ex: carbon black, glass, limestone, talc, etc.
Plasticizers
small molecules that take place between polymer
chains-reduce secondary bonding
Presence of plasticizer transforms brittle polymer to a
ductile one
Commonly added to PVC - otherwise it is brittle
Chapter 15 - 15

Polymer Additives (cont.)


Stabilizers
UV protectants
Lubricants
Added to allow easier processing
polymer slides through dies easier
Colorants
Dyes and pigments
Flame Retardants
Substances containing chlorine, fluorine, and boron

Chapter 15 - 16

Processing of Plastics
Thermoplastic
can be reversibly cooled & reheated, i.e. recycled
heat until soft, shape as desired, then cool
ex: polyethylene, polypropylene, polystyrene.
Thermoset
forms a molecular network (chemical reaction)
degrades (doesnt melt) when heated
a prepolymer molded into desired shape, then
chemical reaction occurs
ex: urethane, epoxy

Chapter 15 - 17

Thermoset
Example:

Two component epoxy glue

Chapter 15 - 18

Processing Plastics Compression Molding


Thermoplastics and thermosets
polymer and additives placed in mold cavity
mold heated and pressure applied
fluid polymer assumes shape of mold

Fig. 15.23, Callister & Rethwisch 9e.


(From F. W. Billmeyer, Jr., Textbook of
Polymer Science, 3rd edition. Copyright
1984 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley &
Sons, Inc.)

Chapter 15 - 19

Processing Plastics Injection Molding


Thermoplastics and some thermosets
when ram retracts, plastic pellets drop from hopper into barrel
ram forces plastic into the heating chamber (around the
spreader) where the plastic melts as it moves forward
molten plastic is forced under pressure (injected) into the mold
cavity where it assumes the shape of the mold
Fig. 15.24, Callister & Rethwisch 9e.
(From F. W. Billmeyer, Jr., Textbook of
Polymer Science, 3rd edition. Copyright
1984 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley &
Sons, Inc.)

Barrel
https://www.youtube.com/watch?v=eUthHS3MTdA
Chapter 15 - 20

Processing Plastics Extrusion


thermoplastics
plastic pellets drop from hopper onto the turning screw
plastic pellets melt as the turning screw pushes them
forward by the heaters
molten polymer is forced under pressure through the
shaping die to form the final product

Fig. 15.25, Callister & Rethwisch 9e.


(Reprinted with permission from Encyclopdia
Britannica, 1997 by Encyclopdia Britannica, Inc.)

Chapter 15 - 21

Processing Plastics Blown-Film


Extrusion

Fig. 15.26, Callister & Rethwisch 9e.


(Reprinted with permission from Encyclopdia
Britannica, 1997 by Encyclopdia Britannica, Inc.)

Chapter 15 - 22

Polymer Types Fibers


Fibers - length/diameter >100
Primary use is in textiles.
Fiber characteristics:
high tensile strengths
high degrees of crystallinity
Nylon:
https://www.youtube.com/watch?v=yFEHKRdXb9Y
Formed by spinning
extrude polymer through a spinneret (a die
containing many small orifices)
the spun fibers are drawn under tension
leads to highly aligned chains - fibrillar structure
Chapter 15 - 23

Polymer Types Miscellaneous

Coatings thin polymer films applied to surfaces i.e.,


paints, varnishes
protects from corrosion/degradation
decorative improves appearance
can provide electrical insulation
Adhesives bonds two solid materials (adherands)

Films produced by blown film extrusion

Foams gas bubbles incorporated into plastic


https://www.youtube.com/watch?v=xjap74m4228

Chapter 15 - 24

Advanced Polymers
Ultrahigh Molecular Weight Polyethylene (UHMWPE)
Molecular weight ca. 4 x 106 g/mol
Outstanding properties

high impact strength


resistance to wear/abrasion
low coefficient of friction
self-lubricating surface

UHMWPE

Important applications
bullet-proof vests
golf ball covers
hip implants (acetabular cup)

Adapted from chapteropening photograph,


Chapter 22, Callister 7e.

Chapter 15 - 25

Advanced Polymers
Thermoplastic Elastomers
Styrene-butadiene block copolymer
hard
component
domain

styrene

butadiene
Fig. 15.21(a), Callister & Rethwisch 9e.

soft
component
domain
Fig. 15.22, Callister & Rethwisch 9e.

Chapter 15 - 26

Summary
Limitations of polymers:

-- E, y, Tapplication are generally small.


-- Deformation is often time and temperature dependent.
Thermoplastics (PE, PS, PP, PC):
-- Smaller E, y, Tapplication
-- Easier to form and recycle
Table 15.3 Callister &
Elastomers (rubber):
Rethwisch 9e:
-- Large reversible strains!
Thermosets (epoxies, polyesters):
Good overview
-- Larger E, y, Tapplication
of applications
and trade names
of polymers.

Chapter 15 - 27

Summary
Polymer Processing
-- compression and injection molding, extrusion,
blown film extrusion

Polymer melting and glass transition temperatures


Polymer applications
-- elastomers
-- fibers
-- coatings
-- adhesives
-- films
-- foams
-- advanced polymeric materials

Chapter 15 - 28

Reminders
Homework V Assignment
12.4, 12.5, 13.8, 13.21
Due: Wednesday April 15th, 2015

Exam III: Wednesday April 22nd, 2015


Chapter 11, 12, 13, 14, 15, 16

Chapter 16 - 1

Chapter 16: Composites


ISSUES TO ADDRESS...
What are the classes and types of composites?
What are the advantages of using composite
materials?
How do we predict the stiffness and strength of the
various types of composites?

Chapter 16 - 2

Composite
Combination of two or more individual
materials
Design goal: obtain a more desirable
combination of properties
e.g., low density and high strength

Chapter 16 - 3

Terminology/Classification
Composite:
-- Multiphase material

Phase types:
-- Matrix - is continuous
-- Dispersed - is discontinuous and
surrounded by matrix

Adapted from Fig. 16.1(a),


Callister & Rethwisch 9e.

Chapter 16 - 4

Terminology/Classification
Matrix phase:

woven
fibers

-- Purposes are to:


- transfer stress to dispersed phase
- protect dispersed phase from
environment

-- Types:

0.5 mm

MMC, CMC, PMC

metal

ceramic

Dispersed phase:
-- Types: particle, fiber

polymer

cross
section
view

0.5 mm
Reprinted with permission from
D. Hull and T.W. Clyne, An
Introduction to Composite Materials,
2nd ed., Cambridge University Press,
New York, 1996, Fig. 3.6, p. 47.

Chapter 16 - 5

Chapter 16 - 6

Chapter 16 -

Boeing 787 Dreamliner

http://www.boeing.com/

http://www.reinforcedplastics.com/
http://www.dailytech.com/

https://www.youtube.com/watch?v=f07HpUAuWgk

Chapter 16 - 8

Classification of Composites
Composites
Particle-reinforced
Largeparticle

Dispersionstrengthened

Fiber-reinforced
Continuous
(aligned)

Structural

Discontinuous
(short)
Aligned

Randomly
oriented

Laminates

Sandwich
panels

Adapted from Fig. 16.2,


Callister & Rethwisch 9e.

Chapter 16 - 9

Classification: Particle-Reinforced (i)


Particle-reinforced
Examples:
- Spheroidite matrix:
ferrite ()
steel

Fiber-reinforced

(ductile)

60 m

- WC/Co
cemented
carbide

matrix:
cobalt
(ductile,
tough)
:

Structural
particles:
cementite
(Fe C)
3
(brittle)
particles:
WC
(brittle,
hard)

Fig. 11.19, Callister &


Rethwisch 9e.
(Copyright 1971 by United
States Steel Corporation.)

Fig. 16.4, Callister &


Rethwisch 9e.
(Courtesy of Carboloy
Systems Department,
General Electric Company.)

600 m

- Automobile matrix:
tire rubber rubber

(compliant)
0.75 m

particles:
carbon
black
(stiff)

Fig. 16.5, Callister &


Rethwisch 9e.
(Courtesy of Goodyear Tire
and Rubber Company.)

Chapter 16 - 10

Classification: Particle-Reinforced (ii)


Particle-reinforced

Fiber-reinforced

Structural

Concrete gravel + sand + cement + water


- Why sand and gravel? Sand fills voids between gravel particles

Reinforced concrete Reinforce with steel rebar or remesh


- increases strength - even if cement matrix is cracked

http://www.rebartool.com/

Chapter 16 - 11

Classification: Particle-Reinforced (iii)


Particle-reinforced

Fiber-reinforced

Structural

Elastic modulus, Ec, of composites:


-- rule of mixture:

upper limit: Ec = Vm Em + Vp Ep

E(GPa)
350
Data:
Cu matrix 300
w/tungsten 250
particles
200
150

(Cu)

Fig. 16.3, Callister &


Rethwisch 9e.
(Reprinted with permission
from R. H. Krock, ASTM
Proceedings, Vol. 63, 1963.
Copyright ASTM International,
100 Barr Harbor Drive, West
Conschohocken, PA 19428.)

20 40 60 80

10 0 vol% tungsten

(W)

Application to other properties:


-- Electrical conductivity, e: Replace Es in equation with es.
-- Thermal conductivity, k: Replace Es in equation with ks.
Chapter 16 - 12

Classification: Fiber-Reinforced (i)


Particle-reinforced

Fiber-reinforced

Structural

Fibers very strong in tension


Provide significant strength improvement to the
composite
Ex: fiber-glass - continuous glass filaments in a
polymer matrix
Glass fibers
strength and stiffness

Polymer matrix
holds fibers in place
protects fiber surfaces
transfers load to fibers

Chapter 16 - 13

Classification: Fiber-Reinforced (ii)


Particle-reinforced

Fiber-reinforced

Structural

Fiber Types
Fibers
polycrystalline or amorphous
generally polymers or ceramics
Ex: alumina, aramid, boron, UHMWPE
Wires
metals steel, molybdenum, tungsten

Chapter 16 - 14

Longitudinal
direction

Fiber Alignment
Fig. 16.8, Callister &
Rethwisch 9e.

Transverse
direction

aligned
continuous

aligned
random
discontinuous
Chapter 16 - 15

Classification: Fiber-Reinforced (iii)


Particle-reinforced
Fiber-reinforced
Aligned Continuous fibers
Examples:
-- Metal: (Ni3Al)-(Mo)
by eutectic solidification.

matrix: (Mo) (ductile)

Structural

-- Ceramic: Glass w/SiC fibers


formed by glass slurry
Eglass = 76 GPa; ESiC = 400 GPa.
From F.L. Matthews and R.L.
Rawlings, Composite Materials;
Engineering and Science, Reprint
ed., CRC Press, Boca Raton, FL,
2000. Used with permission of CRC
Press, Boca Raton, FL.

2 m

fibers: (Ni3Al) (brittle)


From W. Funk and E. Blank, Creep
deformation of Ni3Al-Mo in-situ composites",
Metall. Trans. A Vol. 19(4), pp. 987-998,
1988. Used with permission.
Chapter 16 - 16

Classification: Fiber-Reinforced (iv)


Particle-reinforced
Fiber-reinforced
Discontinuous fibers, random in 2 dimensions
Example: Carbon-Carbon
-- carbon fibers embedded
in polymer resin matrix,
(b)

Structural
C fibers:
very stiff
very strong

C matrix:
less stiff
view onto plane less strong
500 m

-- uses: disk brakes, gas


turbine exhaust flaps,
missile nose cones.
(a)

fibers lie
in plane

Other possibilities:
-- Discontinuous, random 3D
-- Discontinuous, aligned

Adapted from F.L. Matthews and R.L. Rawlings,


Composite Materials; Engineering and Science,
Reprint ed., CRC Press, Boca Raton, FL, 2000.
(a) Fig. 4.24(a), p. 151; (b) Fig. 4.24(b) p. 151.
(Courtesy I.J. Davies) Reproduced with
permission of CRC Press, Boca Raton, FL.
Chapter 16 - 17

Composite Stiffness:
Longitudinal Loading
Continuous fibers - Estimate fiber-reinforced composite
modulus of elasticity for continuous fibers

Longitudinal deformation

c = mVm + fVf
volume fraction

Ecl = EmVm + Ef Vf

and

ec = em = ef
isostrain

Ecl = longitudinal modulus

c = composite
f = fiber
m = matrix
Chapter 16 - 18

Fig_16-9

Chapter 16 -

Composite Production Methods (i)


Pultrusion

Continuous fibers pulled through resin tank to impregnate fibers with


thermosetting resin
Impregnated fibers pass through steel die that preforms to the desired shape
Preformed stock passes through a curing die that is
precision machined to impart final shape
heated to initiate curing of the resin matrix

Fig. 16.13, Callister & Rethwisch 9e.

Chapter 16 - 20

Composite Production Methods (ii)


Filament Winding
Continuous reinforcing fibers are accurately positioned in a predetermined
pattern to form a hollow (usually cylindrical) shape
Fibers are fed through a resin bath to impregnate with thermosetting resin
Impregnated fibers are continuously wound (typically automatically) onto a
mandrel
After appropriate number of layers added, curing is carried out either in an
oven or at room temperature
The mandrel is removed to give the final product
Fig. 16.15, Callister & Rethwisch 9e.
[From N. L. Hancox, (Editor), Fibre Composite Hybrid
Materials, The Macmillan Company, New York, 1981.]

Chapter 16 - 21

Classification: Structural
Particle-reinforced

Fiber-reinforced

Structural

Laminates -- stacked and bonded fiber-reinforced sheets


- stacking sequence: e.g., 0/90

Sandwich panels

Adapted from
Fig. 16.16,
Callister &
Rethwisch 8e.

-- honeycomb core between two facing sheets


- benefits: low density, large bending stiffness
face sheet
adhesive layer
honeycomb
Fig. 16.18, Callister & Rethwisch 9e.
(Reprinted with permission from Engineered
Materials Handbook, Vol. 1, Composites,
ASM International, Materials Park, OH, 1987.)

Chapter 16 - 22

Summary
Composites types are designated by:
-- the matrix material (CMC, MMC, PMC)
-- the reinforcement (particles, fibers, structural)

Composite property benefits:


-- MMC: enhanced E, , creep performance
-- CMC: enhanced toughness
-- PMC: enhanced E/, y, TS/

Particulate-reinforced:
-- Types: large-particle and dispersion-strengthened
-- Properties are isotropic

Fiber-reinforced:
-- Types: continuous (aligned)
discontinuous (aligned or random)
-- Properties can be isotropic or anisotropic

Structural:
-- Laminates and sandwich panels
Chapter 16 - 23