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CE 433/534: Materials Science and Corrosion Structure of Materials Understanding

Lecture 17: Structures & Properties of Ceramics Electrons

configuration in
Bonding
structures among
Assemblies of atoms
(crystal structures/unit
and Polymer (I) atoms atoms cells)

Liquid Solid Gas

Imperfection and Phase diagrams Failure and

Mechanical and other
diffusion in solid and phase strengthening
functional properties
materials transformation mechanisms

Chong Cheng
Department of Chemical & Biological Engineering Ceramics Metals Polymers
Email: ccheng8@buffalo.edu; Phone: 716-645-1193
Electrochemical
Office: 312 Furnas Hall corrosion and
Office Hours: T & R 2-3:20 pm prevention
1 Composites 2

Review of Ceramics Advantages of Ceramics over Metals

• Inexpensive and sustainable: earth abundant elements

• Please cite three advantages of ceramics
over metallic materials.
• Please give two disadvantages of
ceramics over metallic materials.
• What is the coordination number in crystal
structures of ceramics?
for sustainability, e.g., Na, Ca, Al, Si, C
• Electrical and thermal insulators:
• Semiconductor behavior: chips and computers--
indispensable for our modern life
• Chemical stability: Inert and high corrosion-resistances

• What are the two key factors to decide the • Exceptional mechanical properties: Higher hardness
crystal structures of ceramics? and Yield strength
• Excellent high-temperature behavior: withstanding

What about downsides of ceramics?

3 4

Ionic and Covalent Bonds Ceramic Crystal Structures

Ionic Bonding

Metals

Covalent Bonding Ceramic

CsCl ZnS NaCl

– Oxygen anions much larger than metal cations

– Close packed oxygen in a lattice (usually FCC_74% or BCC_68% Atomic
Packing factor)
SP3 hybridation – Cations in the holes of the oxygen lattice
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Stoichiometry Size Effects

Anions are larger than the cations. The
anions are likely packing with a close
• Charge Neutrality: packed arrangement with the cations
--Net charge in the F- occupying the vacant interstices
structure should CaF 2 : Ca 2+ +
cation anions Size - Stable structures:
be zero.
Maximize the number of nearest
F- oppositely charged neighbors to stabilize
the structure with minimum energy.
NaCl Cu2O

The bonding forces should be maximized by packing as

many anion as possible around each cation

Coordination Number and Ionic Radii Silicate Ceramics

r cation
Coordination number increases with r A silicate is a compound containing an anion SiO44− or its
anion compounds. Important members are the cyclic and single chain
How many anions can you arrange around a cation? silicates {[SiO3]2−}n
r cation Coordination Structure
r anion Number Si4+
ZnS
< 0.155 2 linear (zincblende)
O2-
0.155 - 0.225 3 triangular
NaCl
4 TD (sodium cristobalite
0.225 - 0.414
tetrahedral chloride)
The strong Si-O bond leads to a strong, high melting material
0.414 - 0.732 6 OH (1710ºC for cristobalite)
octahedral
CsCl Cobalt: 1495oC
(cesium
0.732 - 1.0 8 cubic chloride) Nickel: 1453oC
Platinum: 1770oC
Tungsten: 3400oC

Quartz and Glass Structure Clay

• Basic Unit: Clay is a fine-grained natural rock or soil material that
4- Glass is noncrystalline (amorphous) combines one or more clay minerals with traces of metal
SiO4 tetrahedron oxides and organic matter (Al2O3+SiO2, etc.)
SiO2 containing impurity ions such as
Si 4+ Na+, Ca2+, l3+, and B3+
O2-

Na +
• Quartz is crystalline:SiO2:
Si 4+
O2-

Soda Glass 11

Melting points:1670oC Glass transition temperature, Tg

573oC Terra Cotta Army in China 2000 years ago
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Hydro-plasticity of Clay Clay: Drying and Firing

• Clay is inexpensive Layered structure of Kaolinite Clay
• When water is added to clay (Al2Si2O5(OH)4)
-- water molecules fit in between
layered sheets
-- reduces degree of van der Waals
bonding Shear
-- when external forces applied – clay
particles free to move past one
another – becomes hydroplastic

Porcelain

Shear

Cement and Concrete Carbon

Cement (CaO+SiO2, Al2O3) is binder, a substance that sets Diamond Graphite
and hardens and can bind other materials together.

Concrete
Hardening of a paste – paste formed
by mixing cement material with
water

Hardening process – hydration CaO + H2O → Ca(OH)2

(complex chemical reactions Ca(OH) + CO → CaCO + H O
2 2 3 2
involving water and cement
particles)

Ca3SiO4 Ca2SiO5 Ca3Al2O6

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Carbon: Structure and Properties Allotropes of Carbon: NanoCarbon

The same chemistry but different structures and physical properties

Graphite: Hexagonal • Soft

• Excellent
electricity and
thermal
conductors
• Lubricant

• Hardest materials,
• Insulators
• lowest thermal
conductivity
• Unique optical
Diamond: Tetrahedral properties,

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Resources and Societies Classification of Solid Materials

On the basis of Chemistry and Atomic Structures

Metals Ceramics Polymers

The American Carbon Society • Relatively dense
• Strong, stiff, ductile
• Electrical and thermal
http://ceramics.org/
conductors
http://onlinelibrary.wiley.com/journal/10.1111/%28ISSN%291551-2916 • Easy to be corrosive
http://www.americancarbonsociety.org/
• Opaque
http://www.journals.elsevier.com/carbon/ • Magnetic
19
• Organic compounds,( C,
• Oxide, nitrides, carbides
H, O, N, S, P, or Si)
• Hard, Stiff and strong,
• Large molecular
extreme brittleness (lack
• Low density,
of ductility,
• Not stiff or strong, ductile
• Insulator of heat and
and plastic
electricity
• Poor thermal stability
• High corrosive resistance
• Low electrical
conductivity

Polymers Advantages of Polymers over Others

CH4 Corrosion Resistance: more weather resistant than metal products.
Insulation: electrical and thermal
Chemical Resistance: Since plastic is impervious to many chemical
compounds, plastic is an ideal material for a wide variety of solution tanks.
Strength: Plastic parts may be designed to be impact and dent resistant.
Economical: Plastic is lighter weight for better fuel economy and cheaper
to manufacture than metal parts.
Coloring: very easy to be coloring; a uniform, maintenance free and cost
effective color for parts.
Certain kinds of polymers provide elasticity (stretching): tires
Easy to be shaped and cut:

A polymer is a large molecule, or macromolecule (with

hundreds to millions of atoms, generally nonmetal such
as C, H, O, S, P, F, Cl, Si), composed of many repeated
subunits. With broad range of properties
21 22

Category of Polymers Natural Polymers-Biomass

Natural polymer: available directly Silk
from nature. They are often water-
based. Examples of naturally occurring
polymers are wool, leather, rubber,
DNA, cellulose, and proteins.
Natural polymers:
Synthetic polymers:
DNA
Cotton Chitin Wool Rubber

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Cellulose Natural Rubber

• Cellulose is a highly abundant organic compound. Extensive
hydrogen bonding between the chains causes native cellulose
to be roughly 70% crystalline. It also raises the melting point
(>280 oC) to above its combustion temperature.
• Cellulose serves as the principal structural component of green
plants and wood.
• Cotton is one of the purest forms of cellulose and has been
cultivated since ancient times.
• Cotton also serves (along with treated wood pulp) as the
source the industrial production of cellulose-derived materials
which were the first "plastic" materials of commercial
importance.
• A variety of plants produce a sap consisting of a colloidal
dispersion of cis-polyisoprene. This milky fluid is
especially abundant in the rubber tree (Hevea); it drips
when the bark is wounded.
• After collection, the latex is coagulated to obtain the solid
rubber. Natural Rubber is thermoplastic, with a glass
transition temperature of –70°C.
• Raw natural rubber tends to be sticky when warm and
brittle when cold, so it was little more than a novelty
material when first introduced in Europe around 1770.
• It did not become generally useful until 1844 when Charles
Goodyear found that heating it with sulfur — a process
he called Vulcanization — could greatly improve its
properties. (vulcanization = crosslinking)
cis-polyisoprene

Synthetic Polymer Polymer Structures

Synthetic polymer: Synthetic polymers are derived mainly from Poly mer
petroleum oil, and made by scientists and engineers. many repeat unit
Examples of synthetic polymers include nylon, polyethylene,
polyester, Teflon, and epoxy. Cellulose
• Thermoplastics: becomes pliable or moldable above a specific
temperature and solidifies upon cooling
• Thermosets: contrast with thermoplastic polymers, do not soften when
heated Rubber
• Elastomers: recovering their original shape after being stretched to great
extents
• Synthetic fibers: fibers have high strength (than plastics and repeat repeat repeat
elastomers) are created by forcing, usually through extrusion, fiber unit unit unit
forming materials through holes H H H H H 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 C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3

Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

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Polymer Chemistry Unsaturated Monomer

Saturated hydrocarbons are hydrocarbons that contain only
In polymer chemistry, polymerization is a process of reacting single bonds between carbon atoms. Each carbon bonded to
monomer molecules together in a chemical reaction to form four other atoms Single bond
polymer chains or three-dimensional networks
H H
H
C C

H H
H

Unsaturated Hydrocarbons: Unsaturated hydrocarbons are

hydrocarbons that have double or triple covalent bonds
between adjacent carbon atoms.
Triple bond
Double bond
H H acetylene
C C H C C H
H H ethylene
29 Double & triple bonds relatively reactive – can form new bonds30

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Addition polymerization Monomer Structures of Addition Polymers

Chain-growth polymerization or Addition polymerization is a polymerization
technique where unsaturated monomer molecules add onto the active site of a
growing polymer chain one at a time. Growth of the polymer occurs only at one (or
possibly more) ends. Addition of each monomer unit regenerates the active site
Free radical polymerization
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer An addition polymer is a polymer which is formed by an
Initiator: example - benzoyl peroxide
addition reaction, where many monomers bond together via
H H H rearrangement of bonds without the loss of any atom or
C O O C 2 C O =2 R molecule. 32
H H H

Some Common Addition Polymers Condensation (Step) Polymerization

Condensation polymers are any kind of polymers formed through a
condensation reaction—where molecules join together—losing small
molecules as by-products such as water or methanol, as opposed to
addition polymers which involve the reaction of unsaturated monomers.
Types of condensation polymers include polyamides, polyacetals and
polyesters.

Normally, two or more different monomers are used in the

reaction. They often have symmetrical structures

Some Condensation Polymers Molecular Weight

Paraffin wax
Molecular weight: 768 Melt point 37 oC

Polyethylene
melting point: 120 to 140oC

Molecular weight: thousands to millions

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Molecular Weight Polymers – distribution of chain sizes

Polymers – distribution of Pt nanoparticle –distribution

chain sizes of particle sizes

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Average Molecular Weight Average Molecular Weight

Number-average Weight-average
molecular weight molecular weight
Molecular weight, Mi: Mass of a mole of chains (g/mol).
0.30
0.28
Lower M higher M

Number percent
How many molecule having
specified molecular weight of Mi Weight
number 100 100
= Total number of molecule fraction molecule
fraction
Gram

Weight percent
How much weight is contributed from polymer
with specified molecular weight of Mi There are 28 molecules having There is 30 g polymer molecules
= Total weight of polymer
molecular weight of 25 g/mol having molecular weight of 25 g/mol

mixture

Molecular Weight Calculation Molecular Weight Calculation

Mixture polymer = a group of people Mixture polymer = a group of people
One Molecule = one Person One Molecule = one Person
Molecular Weight = Person Weight Molecular Weight = Person Weight
Ni Mi xi wi Ni Mi xi wi
100/1860 100/1860
# of people mass (lb) # of people mass (lb)
120/1860 120/1860
1 100 0.1 0.054 1 100 0.1 0.054
1
2
120
140
0.1
0.2
0.065 M n 
0.151

xi Mi 1
2
120
140
0.1
0.2
0.065 M n 
0.151

xi Mi
3 180 0.3 0.290 3 180 0.3 0.290
2
1
220
380
0.2
0.1
0.237
0.204 
M w  w i Mi
2x220/1860
2
1
220
380
0.2
0.1
0.237
0.204 
M w  w i Mi
2x220/1860

Total: 10 1860 380/1860 Total: 10 1860 380/1860

Mn Mw Mn Mw
1860 =1x100+1x120+2x140+3x180+2x220+1x380 186 lb 216 lb 1860 =1x100+1x120+2x140+3x180+2x220+1x380 186 lb 216 lb

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Summary Degree of Polymerization (DP)

• Polymerization reactions including n = number of repeat units per chain

H H H H H H H H H H H H
addition and condensation ones. H C C (C C ) C C C C C C C C H ni = 6
H H H H H H H H H H H H
• What is the monomer.
Mn
• Know how to compute the number- and DP   xi ni 
m
weight- average molecular weight, as well
Number-average molecular weight
as the degree of polymerization
m: molecular weight of repeat unit

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Excise I
The following table lists molecular weight data for a poly(tetrafluoroethylene) (a) From the tabulated data, we are asked to compute M n
(PTFE) material. Compute the following:
(a) the number-average molecular weight
(b) the weight-average molecular weight , the number-average molecular weight. This is carried out below.
Molecular wt
Molecular Weight Range Mean Mi xi xiMi
Range (g/mol) xi wi 10,000-20,000 15,000 0.03 450
10,000–20,000 0.03 0.01 20,000-30,000 25,000 0.09 2250
20,000–30,000 0.09 0.04 30,000-40,000 35,000 0.15 5250
40,000-50,000 45,000 0.25 11,250
30,000–40,000 0.15 0.11
50,000-60,000 55,000 0.22 12,100
40,000–50,000 0.25 0.23
60,000-70,000 65,000 0.14 9100
50,000–60,000 0.22 0.24 70,000-80,000 75,000 0.08 6000
60,000–70,000 0.14 0.18 80,000-90,000 85,000 0.04 3400
70,000–80,000 0.08 0.12 ____________________________

å x M = 49,800 g/mol
80,000–90,000 0.04 0.07
Mn = i i
The best-known brand name of PTFE-based formulas is
Teflon by DuPont Co., which discovered the compound. 45 46

Mw
(b) From the tabulated data, we are asked to compute
(c) Now we are asked to compute the degree of polymerization, which is
, the weight-average molecular weight. This computation is carried out below.
possible using Equation 14.6. The polytetrafluoroethylene the repeat unit
consists of 2 carbon atoms and 4 fluorine atoms; therefore, its repeat unit
Molecular wt. molecular weight is equal to
Range Mean Mi wi wiMi m = 2(AC) + 4(AF) = (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol
10,000-20,000 15,000 0.01 150
20,000-30,000 25,000 0.04 1000
30,000-40,000 35,000 0.11 3850 Thus, using Equation 14.6 we compute the degree of polymerization as
follows:
40,000-50,000 45,000 0.23 10,350
50,000-60,000 55,000 0.24 13,200
60,000-70,000 65,000 0.18 11,700 M n 49,800 g/mol
70,000-80,000 75,000 0.12 9000 DP = = = 498
80,000-90,000 85,000 0.07 5950 m 100.02 g/mol
___________________________

Mw = åw M i i = 55,200 g/mol
47 48

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Summary Summary

• Ceramic materials have covalent & ionic bonding.

• Structures are based on:
• Polymerization reactions including
-- charge neutrality
addition and condensation ones.
-- maximizing # of nearest oppositely charged neighbors.
• What is the monomer. • Structures may be predicted based on:
-- ratio of the cation and anion radii.
• Know how to compute the number- and
weight- average molecular weight, as well • Room T mechanical response is elastic, but fracture
as the degree of polymerization is brittle, with negligible deformation.
• Elevated T creep properties are generally superior to
those of metals.

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Ceramics Application: Cutting Tools Ceramics Application: Sensors

• Example: ZrO2 as an oxygen sensor

Ca 2+
• Tools: • Principle: Increase diffusion rate of oxygen
-- for grinding glass, tungsten, to produce rapid response of sensor signal to
carbide, ceramics change in oxygen concentration
-- for cutting Si wafers • Approach: A substituting Ca2+ ion
-- for oil drilling removes a Zr 4+ ion and
Add Ca impurity to ZrO2: an O2- ion.
• Materials: -- increases O2- vacancies
oil drill bits blades -- increases O2- diffusion rate
-- manufactured single crystal
or polycrystalline diamonds Single crystal • Operation:
diamonds sensor
in a metal or resin matrix. -- voltage difference produced when
gas with an
-- polycrystalline diamonds O2- ions diffuse from the external unknown, higher reference
polycrystalline gas at fixed
surface through the sensor to the oxygen content O2-
resharpen by microfracturing oxygen content
diamonds in a resin diffusion
along cleavage planes. reference gas surface.
matrix.
-- magnitude of voltage difference
Photos courtesy Martin Deakins,
GE Superabrasives, Worthington,  partial pressure of oxygen at the + -
OH. Used with permission.
external surface voltage difference produced!

51 52

Refractories Advanced Ceramics:

Materials for Automobile Engines
• Materials to be used at high temperatures (e.g., in
high temperature furnaces).
• Consider the Silica (SiO2) - Alumina (Al2O3) system. • Advantages: • Disadvantages:
• Silica refractories - silica rich - small additions of alumina – Operate at high – Ceramic materials are
depress melting temperature (phase diagram): temperatures – high brittle
efficiencies – Difficult to remove internal
2200 – Low frictional losses voids (that weaken
3Al2O3-2SiO2
T(ºC) – Operate without a cooling structures)
mullite – Ceramic parts are difficult
2000 Liquid system
(L) alumina + L to form and machine
– Lower weights than
1800 current engines
crystobalite mullite alumina
+L +L +
Fig. 12.27, Callister &

1600 mullite
Rethwisch 8e. (Fig. 12.27
adapted from F.J. Klug and • Potential candidate materials: Si3N4, SiC, & ZrO2
mullite R.H. Doremus, J. Am. Cer.
+ crystobalite Soc. 70(10), p. 758, 1987.) • Possible engine parts: engine block & piston coatings
1400
0 20 40 60 80 100
Composition (wt% alumina)
53 54

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Isomers Stereoisomers
Stereoisomers are isomeric molecules that have the same
molecular formula and sequence of bonded atoms
(constitution), but that differ only in the three-dimensional
orientations of their atoms in space H H
H H
C C C C
H R
H R

A A

C C
E E
B D D B

mirror plane
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cis/trans Isomers Structural Isomers

Cis/trans isomerism (geometric isomerism, configurational Structural Isomerism: two compounds with same
isomerism) is a term used to refer to the stereoisomerism chemical formula can have quite different structures
engendered in the relative orientation of functional groups within a
molecule Ex: C8H18
cis/trans • n-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

cis trans • 2-methyl-4-ethyl pentane (isooctane)

CH3
cis-isoprene trans-isoprene
H3C CH CH2 CH CH3
(natural rubber) (gutta percha)
CH2
bulky groups on same bulky groups on opposite CH3
side of chain sides of chain

Tacticity

Tacticity – stereoregularity of chain

H H H H H H H H
isotactic – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R

H H H R H H H R
syndiotactic – R groups
C C C C C C C C
alternate sides
H R H H H R H H

H H H H H R H H
atactic – R groups random C C C C C C C C
H R H R H H H R

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