Chapter 6 – Ceramics and Carbon

Materials
Pivotal Questions:
- What are ceramic materials?
- What are the industrial uses of ceramics?
- What happens to ceramic materials at the end of
their useful lives?
- Is graphite a ceramic or a polymer?
- Do other carbon materials offer unusual
properties?
Ceramics
 Ceramics are compounds containing both
metallic and non-metallic atoms
 Name comes from the Greek word Keramos
meaning pottery
 Ceramics cover a wide range of materials
from glasses to cement to body armor
 Blend of ionic and covalent bonds provide
most ceramics with hardness and stability
If the bonding is primarily ionic
 Small cations bonds with larger anions

 The net charge of the system must balance, so that a

system comprised of titanium cations (Ti4+) in a lattice
with oxygen (O2-) anions, there must be twice as many
oxygen atoms as titanium atoms
Coordination Numbers
 The Coordination Number
is the number of cations that
each anion touches
 It is controlled by atomic
radii and geometry
 The ratio of atomic radii
determines the stability of
coordination numbers
Ionic ratios for stable coordination
numbers
Classification of Ceramic Systems
 AX-Systems – simplest structure consisting of equal
numbers of one cation species and one anion species
 AmXp-Systems – Structure where the cation and anion
species have different charges
 AmBnXp –Systems – System with two diffent cation
species (A and B)

 Interstitial voids in the lattice structures become very

important because atoms or ions can occupy the
openings
 Octahedral and tetrahedral
positions
 The FCC-structure common
to many ceramics has two
distinct types of interstitial
sites.
 Four Tetrahedral Positions
exist at the points where the
three atoms in one plane
come in contact with a fourth
atom in an adjacent plane
 Eight Octahedral Positions
exist in the top and bottom
faces such that six atoms are
equidistant from the spaces
Sodium Chloride Structure
 One of the most common
AX-systems
 Chlorine anions occupy the
corner and face sites of the
FCC-lattice
 Sodium anions occupy
interstitial sites
 Because each sodium ion
contacts six chlorine ions, the
coordination number is 6
 Iron oxide (FeO) and
manganese sulfate (MnS) also
have this structure
Zinc-blend structure
 Another AX-system
 Two versions exist
 In the first (as shown), anions
fill the corner and face
positions of the FCC lattice
with anions in the tetrahedral
sites
 The same systems exists with
the cations and anions
reversed
 Coordination number is 4
 Silicon Carbide also forms a
zinc-blend structure
Calcium Fluoride (CaF2) Structure
 An AmXp-system with
calcium ions occupying the
lattice sites in an FCC-system
and fluorine anions filling
the tetrahedral sites.
 The octahedral sites are
unoccupied
 In Uranium oxide (UO2), the
unoccupied spaces trap
fissionable byproducts
Perovskite Structure
 An AmBnXp– system with two
cations that may have
different charges
 A metallic ion capable of
holding a large charge filling
the octahedral interstitial site
 The other metallic ion fills
the corners with the cations
filling the six faces
 Perovskite materials display
piezoelectric properties
Spinel Structure
 Another AmBnXp– system
 In the MgAl2O4 system
shown on the right,
magnesium cations fill the
four tetrahedral sites;
aluminum cations occupy the
eight octahedral sites, and
the oxide anions fill the
corners and faces
 Materials with the spinel
structure display
ferromagnetic properties
 Phase Diagrams for Ceramic
Systems
 Ceramic systems are
represented by phase
diagrams, just like metal
alloys
 The same principles of
interpreting phase diagrams
apply including
 Calculation of phase
compositions
 Tie-lines
 Invariant points
 Solidus, liquidus, and solvus
lines
Industrial Uses of Ceramics
 The American Ceramic Society classifies ceramics into
seven distinct groups:
 Abrasives
 Glasses
 Cements
 Refractories
 Structural Clay Products
 Whitewares
 Advanced Ceramics
 Each group possesses distinct properties and
challenges
Abrasives
 Abrasives are used to wear away other materials
through processes like sanding, grinding, lapping, and
pressure blasting
 The abrasive particle acts as a cutting instrument,
ripping away parts of the softer material
 Hardness is the most important property in an
abrasive
 Friable materials form sharp edges when they break
under stress from heat and pressure
Sandpaper
 Most familiar abrasive
product with hard particles
bonded to a backing by a
resin
 Earliest sandpaper dates back
to 13th-century China where
seashell fragments were
bonded with natural gums to
shark skins or parchments
 Modern sandpaper is
classified based on grit size
(number of abrasive particles
per square inch)
Abrasives used in sandpaper
 Four distinct types of abrasives are used in sandpaper
 Alumina
 Garnet
 Silicon carbide
 “Ceramic”
 Each material is used for different tasks
Alumina (Al2O3)
 The most common abrasive is
friable, tough, hard (9 on the
Moh scale), dense, and
inexpensive
 Alumina forms the corundum
(HCP) structure shown on
the right
 Many gemstones are alumina
with specific impurities like
Chromium ions providing the
red color in rubies
Other Sandpaper Abrasives
 Garnet – A variety of materials with an A3B2(SiO4)3
structure. It is not friable and less hard than alumina
but produces a smoother surface and seals off the grain
of the wood.
 Silicon Carbide – Exceptional hard and friable
material ideal for sanding metal, plaster, and fiberglass
 Ceramic – hardest and most expensive abrasive in
which hard particles are deposited on a backing
through a sol-gel process. Generally found on belt
sanders used to level and shape wood.
Powder Pressing
 Unlike polymers and metals, ceramics cannot be
formed by melting and pouring through a die or into a
mold.
 Particles are mixed with a binding agent (usually
water) that lubricates them during compaction and
forced into a shape under pressure
 In uniaxial powder pressing, the ceramic powder is
compressed in a single direction by a metal die
 In isotactic powder pressing, the ceramic material is
placed in a rubber chamber and hydrostatic pressure is
used to apply uniform pressure in all directions
Sintering
 The fused particles produced in powder pressing must
be sintered to improve properties
 The particles are heated, causing the grain boundaries
between them to coalesce.
 The interstitial regions shrink and eventually form
small spherical pores

Sintering
Silica Glasses
 Non-crystalline material
made from crystalline SiO2
 When a-quartz is heated it
undergoes a series of phase
transformation and
eventually melts
 The high viscosity of molten
silica prevents the molecules
from aligning into the
energetically favored b-
cristoballite form.
Silica Structure
 The basic structure of glass is
based on the SiO44-
tetrahedron shown on the
right.
 The silicon atom sits in the
center with oxygen in each
corner
 The silicon-oxygen bonds
possess both ionic and
covalent characteristics
Loose Networks
 Although there is no large-
scale crystalline order in the
glass, the tetrahedra form a
loose network with corner to
corner contact
 A typical loose network is
pictured at the right
Additives to Glasses
 Network modifiers – metal
oxides added to reduce the
viscosity of the loose networks.
Oxygen atoms from the oxides
break up the network by
occupying a tetrahedral site.
 Intermediate Oxides –
molecules incapable of forming
their own network, but able to
join the existing loose network.
Used to enhance specific
properties (e.g. - Lead oxide
increases the index of refraction
making the glass more lustrous).
Additives used as coloring agents
Float-Glass Process
 Over 80% of commercial
glass is produced this way
 Constituents are melted in a
furnace
 A fine glass ribbon is drawn
from the furnace and floats
on the surface of the molten
tin
 Tin and glass are immiscible,
so a perfectly smooth surface
forms between them
 The glass is then annealed in
a special furnace called a lehr
Cements
 Cement is a generic term referring to any material
capable of binding things together
 In materials, cement generally refers to two classes of
materials
 Hydraulic cements that require water to form a solid
 Non-hydraulic cements that form a solid without water
 The most common hydraulic cement is Portland
Cement
Portland Cement
 Made from pulverized nodules of sintered calcium
silicates
 Most common use is in the ubiquitous building
material concrete
Composition of Portland Cement
Classes of Portland Cement
Cement Nomenclature
 To characterize the complex series of reactions that
occur in concrete formation, a system of chemical
shorthand has been developed
Four stages of cement production
 Evaporation – Dehydration in which excess water is
driven off
 Calcination in which calcium carbonate is converted
to calcium oxide
 Clinkering in which calcium trisilicates form
 Cooling in which the heated materials return to room
temperature
Evaporation - Dehydration
 A mixture of calcium carbon carbonate (CaCO3),
quartz (SiO2), and clay (Fe2O3 and Al2O3) particles are
mixed in a rotary kiln and heated to between 250°C
and 450°C to drive off all free water.
 As the heating continues to around 600°C, any water
bound to the silicates and oxides is removed.
Calcination
 Begins at approximately 900°C
Clinkering
 Begins around 1450°C and forms calcium silicates

 The emerging product is called clinker and is cooled

and then ground along with powdered gypsum
Calcium silicate reactions
 The Portland cement particles are mixed with water
and undergo a highly exothermic series of reactions

 The calcium silicate hydrates are amorphous particles

with a variety of compositions, so no exact ratio exists
between the components
 Really occur in five stages
Tricalcium aluminate reactions
 Occur at the same time as the calcium silicate
reactions

 The ettringite forms a diffusion barrier around the

calcium aluminate and slows the reaction. Once the
gypsum has been used, the ettringite reacts with the
calcium aluminate
Composition of hardened cement
paste
Microstructure of hardened
cement paste
 C-S-H grows on C3S and C2S
grains and begin to radiate
outward as spikes
 The spikes from adjacent
particles interlock to connect
the grains
 CH forms thick crystalline
plates imbedded within the
larger C-S-H matrix

Cement Formation
Porosity in Cement
 Porosity has a significant impact on the strength of
cement

 Capillary Pores are the open spaces between adjacent

grains

 Gel Pores are spaces within the C-S-H material

Refractories
 Refractories are materials capable of withstanding
high temperatures without melting, degrading, or
reacting with other materials
 Refractory ceramics come in two basic types:
 Clays (which contain at least 12% silica)
 Non-clays
 Fireclay is the most common refractory and is made
from kaolinite (a mixture or alumina and silica)
Alumina-Silica phase diagram
 Fireclay contains 50-70%
silica, 25-40% alumina, and
small amounts of CaO, Fe2O3,
MgO and TiO3.
 The silica adds resistance to
attack by acids
 Bricks do not melt to 1587°C
 High alumina (mullite) bricks
do not melt until 1890°C
 Periclase (90% MgO) bricks
resist alkali attacks and are
used in the steel industry
Structural Clay Products
 Structural clay products
include any ceramic used in
building construction,
especially brick and terra
cotta
 Terra Cotta is made from a
redart clay containing 64%
silica, 16% alumina, 7% iron
oxide, and 4% potassium
oxide
 Nearly $2,000,000,000 of
brick is sold in the US each
year, most for home and
building construction
Whitewares
 Whitewares are fine-textured ceramics used in
dinnerware, floor and wall tiles, and sculpture

 Porcelain is the best known whiteware and is made

mainly of kaolinite, but may also contain glass, bone
ash (calcium phosphate), steatite (a glassy form of
talc), and china stone (a blend of quartz and mica)
Whiteware Processing
 Kaolinite clay is shaped and
allowed to dry
 The material is fired in a kiln
to temperatures greater than
800°C and emerges as a glassy
white material called bisque
(like the pumpkin on the
right)
 Water is driven off during the
heating as well as pores in the
clay provide natural vents
 The conversion is irreversible
Glazing
 Bisque materials are coated with a blend of silica and
metal oxides called glazes and refired at temperatures
between 950°C and 1430°C
 Glazes add color to the bisque
 Glazes also provide an impermeable barrier
 In most commercial products, the application of glazes
is automated, but artisans still apply their own glazes
by hand.
Advanced Ceramics
 Advanced ceramics are engineered materials for use in
high-end applications
 Ceramic armor, ceramic nanoparticles, solid oxide fuel
cells, and bioceramics are primary examples
 Advanced ceramics like boron nitride, titanium nitride,
and boron carbide make excellent armor because of their
exceptional hardness
Ceramic Nanoparticles
 Ceramic particles with sizes ranging from 20-100 nm
are produced through sol-gel and flame aerosol
processes

 Practical applications include:

 Light-sensitive, silica-based nanoparticles are being used to
target tumors in cancer patients
 Barium titanate particles are used in multilayer capacitors
 Silicon carbide nanoparticles are being tested to improve
ceramic armor
Solid oxide fuel cells (SOFCs)
 An SOFC uses electrochemistry to convert chemical
energy to electrical energy similar to the galvanic cells
described in Chapter 4.
 Unlike traditional galvanic cells that require a clean
stream of hydrogen as fuel, SOFCs can use
hydrocarbons
 Nickel oxides serve as the anodic material while
strontium-doped lanthanum chromite is used as the
interconnect material between cells
Bioceramics
 Bioceramics are discussed in greater detail in Chapter
9

 Primary functions include:

 Lubricating surfaces in prosthetics
 Providing clot-resistant coatings on heart valves
 Serving as transfer agents or collectors of radioactive species
in cancer treatments
 Providing a framework to stimulate bone growth
Recycling of Ceramics
 Because ceramics do not corrode, they last far longer
than other materials (the pyramids of Egypt have last
for thousands of years)
 The same resistance makes ceramics difficult to recycle
(except for glass)
 Most discarded ceramics wind up in landfills
 Unwanted Portland Cement products are sometimes
pulverized and used as aggregate for future materials
Glass Recycling
 Discarded glass is collected routinely by many
municipalities
 They are cleaned, sorted by color, and ground into a
fine powder called cullet.
 Cullet is remelted and reformed into new glass
products
 Each ton of cullet used instead of fresh silica saves
more than 600 pounds of carbon dioxide emissions
Carbon Materials
 Carbon materials range from ancient, natural products
to high-end engineering materials.
 Specific carbon materials include:
 Graphite
 Diamond
 Carbon fibers
 Fullerenes
 Carbon nanotubes
Graphite
 Graphite is an allotropic
form of carbon with aromatic
rings in graphene planes with
each layers separated from
the next by 3.35 angstroms
 In-plane strength is
incredibly strong because of
the resonance stabilized
double bonds, but only van
der Waals interactions exist
between planes
 Highest known modulus
(1080 GPa)
Graphite (continued)
 Graphite fits the technical
definition of a polymer since
it consists of covalently
bonded units repeated over
and over
 Graphite behaves like a
ceramic (strong, resistant,
brittle)
 Industrial uses include pencil
“lead” and as cladding in
nuclear reactors and as a
moderator that slows
neutrons in uranium fission
Diamond
 Diamond is an allotropic
form of carbon that forms a
clear FCC structure with
carbon atoms occupying four
of the eight octahedral sites
 They are the hardest natural
material (Moh hardness = 10)
and can be scratched only by
other diamonds
 They are colorless, but can
develop color with the
presence of impurities
Commercial uses of diamond
 Diamonds with suitable color, size, and clarity are used
as gemstones
 Most diamonds are not suitable and over 80% of all
diamonds are classified as bort and used for industrial
applications including:
 Lapping agents
 Saw blades
 Drill bit tips
 Low friction hinges on the space shuttle
Diamond formation
 Natural diamonds form when carbon deposits are
exposed to a blend of extreme temperatures and
pressures for long enough periods of time to allow for
crystal growth
 Most form in volcanic pipes that form from deep
underground eruptions of magma
 These pipes are rare and most diamonds are mined in
central and southern Africa
Synthetic Diamonds
 The utility and rarity of diamonds have led to the
production of synthetics
 The author H.G. Wells speculated about synthetic
diamonds in 1914 in his book The Diamond Maker
 The first synthetics were produced in 1953
 The HPHT method used high pressure and high
temperatures to produce diamonds, but the
equipment is enormous and expensive
 Chemical Vapor Deposition (CVD) assembles a
diamond one atom at a time and offers great promise
Carbon Fibers
 Fibers consisting of at least
92% mass fraction carbon
 Can obtain a wide range of
mechanical, electrical,
chemical, and thermal
properties
 Produced from an organic
precursor in a 3 stage process:
 Stabilization
 Carbonization
 Graphitization
Stabilization
 Most precursor fibers must
be converted to a thermally
stable form that cannot melt
through a process called
stabilization
 The most common precursor,
polyacrylonitrile (PAN) is
converted to a ladder polymer
as shown by heating the
polymer in air at
temperatures between 200°C
and 300°C
Carbonization and graphitization
 Stabilized fibers are the heated in an inert
atmosphere. At temperatures below 2000°C, the
carbonization process occurs. Inorganics and
aliphatic carbons are driven off, leaving graphene
planes behind. The planes are disordered
(turbostratic) and contain many voids
 At temperatures above 2000°C, graphitization
occurs. Crystal growth results in a smoothing of the
turbostratic structure into something approaching the
idealized carbon fiber
Mesophase pitch-based fibers
 Pitch (the residue from
petroleum distillation) that
has experienced a series of
thermal treatments form a
liquid crystalline order
(mesophase)
 Mesophase pitch forms a
carbon fiber that has
exceptional thermal
properties
Properties of Carbon Fibers
Fullerenes (or Buckyballs)
 Fullerenes are newly
discovered allotropic forms of
carbon with 60, 70, 76, or 78
carbon atoms formed into a
cage-like structure
 They are named after
architect Buckminster Fuller,
who developed the geodesic
dome
 The empty cage shape shows
great promise for a variety of
commercial applications
Carbon nanotubes
 Single-wall carbon nanotubes
(SWNTs) are essentially
single graphene planes rolled
into a cylindrical tube
 Carbon SWNTs are an order-
of-magnitude stronger than
steel
 Many experts believe that
they will redefine the
electronic materials industry
Multiwalled nanotubes (MWNTs)
 MWNTs involve multiple
graphene planes rolled, much
like nesting dolls fit inside
one another.
 They are classified based on
unit vectors that define
directions on graphene
planes
 They may be classified as
 Zigzag
 Armchair
 chiral