HANDOUTS 5 – Structure of Ceramics Refractories

◼ Used to provide thermal protection of other

Ceramics - A wide-ranging group of materials whose
materials in very high temperature applications, such as
ingredients are clays, sand and feldspar.
steel making (Tm=1500°C), metal foundry operations,
Clays
etc.
Contain some of the following:
◼ They are usually composed of alumina (Tm=2050°C)
◼ Silicon & Aluminum as silicates
and silica along with other oxides: MgO (Tm=2850°C),
◼ Potassium compounds
Fe2O3, TiO2, etc., and have intrinsic porosity typically
◼ Magnesium compounds
greater than 10% by volume.
◼ Calcium compounds
◼ Specialized refractories, (those already mentioned)
Sand contains Silica and Feldspar or Aluminium
and BeO, ZrO2, mullite, SiC, and graphite with low
Potassium Silicate.
porosity are also used.
Types of Ceramics
Amorphous Ceramics(Glasses)
◼ Whitewares
◼ Main ingredient is Silica (SiO2)
◼ Refractories
◼ If cooled very slowly will form crystalline structure.
◼ Glasses
◼ If cooled more quickly will form amorphous structure
◼ Abrasives
consisting of disordered and linked chains of Silicon and
◼ Cements
Oxygen atoms.
Comparison: metals vs ceramics
◼ This accounts for its transparency as it is the crystal
boundaries that scatter the light, causing reflection.
◼ Glass can be tempered to increase its toughness and
resistance to cracking.
Glass Types
Three common types of glass:
◼ Soda-lime glass - 95% of all glass, windows containers
etc.
◼ Lead glass - contains lead oxide to improve refractive
index
◼ Borosilicate - contains Boron oxide, known as Pyrex.
Bonded Clay Ceramics Glasses
Made from natural clays and mixtures of clays and ◼ Flat glass (windows)
added crystalline ceramics. ◼ Container glass (bottles)
These include: ◼ Pressed and blown glass (dinnerware)
◼ Whitewares ◼ Glass fibres (home insulation)
◼ Structural Clay Products ◼ Advanced/specialty glass (optical fibres)
◼ Refractory Ceramics Crystalline Ceramics
Whitewares Good electrical insulators and refractories.
◼ Crockery ◼ Magnesium Oxide is used as insulation material in
◼ Floor and wall tiles heating elements and cables.
◼ Sanitary-ware ◼ Aluminium Oxide
◼ Electrical porcelain ◼ Beryllium Oxides
◼ Decorative ceramics ◼ Boron Carbide
Refractories ◼ Tungsten Carbide.
 Firebricks for furnaces and ovens. ◼ Used as abrasives and cutting tool tips.
 Have high Silicon or Aluminium oxide content. Abrasives
 Brick products are used in the manufacturing ◼ Natural (garnet, diamond, etc.)
plant for iron and steel, non-ferrous metals, ◼ Synthetic abrasives (silicon carbide, diamond, fused
glass, cements, ceramics, energy conversion, alumina, etc.) are used for grinding, cutting, polishing,
petroleum, and chemical industries. lapping, or pressure blasting of materials
Advanced Ceramics Ceramic Armour
◼ Advanced ceramic materials have been developed ◼ Ceramic armour systems are used to protect military
over the past half century personnel and equipment.
◼ Applied as thermal barrier coatings to protect metal ◼ Advantage: low density of the material can lead to
structures, wearing surfaces, or as integral components weight-efficient armour systems.
by themselves. ◼ Typical ceramic materials used in armour systems
◼ Engine applications are very common for this class of include alumina, boron carbide, silicon carbide, and
material which includes silicon nitride (Si3N4), silicon titanium diboride.
carbide (SiC), Zirconia (ZrO2) and Alumina (Al2O3) ◼ The ceramic material is discontinuous and is
◼ Heat resistance and other desirable properties have sandwiched between a more ductile outer and inner
lead to the development of methods to toughen the skin.
material by reinforcement with fibers and whiskers ◼ The outer skin must be hard enough to shatter the
opening up more applications for ceramics projectile.
◼ Structural: Wear parts, bioceramics, cutting tools, ◼ Most of the impact energy is absorbed by the
engine components, armour. fracturing of the ceramic and any remaining kinetic
◼ Electrical: Capacitors, insulators, integrated circuit energy is absorbed by the inner skin, that also serves to
packages, piezoelectrics, magnets and superconductors contain the fragments of the ceramic and the projectile
◼ Coatings: Engine components, cutting tools, and preventing severe impact with thepersonnel/equipment
industrial wear parts being protected.
◼ Chemical and environmental: Filters, membranes, ◼ Alumina ceramic/Kevlar composite system in sheets
catalysts, and catalyst supports about 20mm thick are used to protect key areas of
Engine Components Hercules aircraft (cockpit crew/instruments and
loadmaster station).
◼ This lightweight solution provided an efficient and
removable/replaceable armour system. Similar systems
used on Armoured Personnel Carrier’s.
Ceramic - Composite Armor

Turbocharger

Armoured Glass
◼ Many have tried to gain access with golf clubs and
baseball bats but obviously the glass remains intact !
From time to time a local TV station intends to show
videos of those trying to get at the cash!!
Silicon Carbide - Body armour and other components
Silicon Carbide - Automotive Components in Silicon
chosen for their ballistic properties.
Carbide. Chosen for its heat and wear resistance
Ceramic Crystal Structures
◼ Oxide structures
◼ oxygen anions larger than metal cations
◼ close packed oxygen in a lattice (usually FCC)
◼ cations fit into interstitial sites among oxygen ions
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:

Factors that Determine Crystal Structure

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

2. Maintenance of Charge Neutrality : --Net charge in

ceramic should be zero. --Reflected in chemical formula:

Coordination # and Ionic Radii

r cation
• Coordination # increases with UNIT CELL ATOM
r anion
RATIO
To form a stable structure, how many anions can
surround around a cation?
 Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure

MgO and FeO

MgO and FeO also have the NaCl structure

AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc
AX-Type Crystal Structures blende
◼ Rock Salt Structure - The Cesium Chloride structure:
coordination number for both cations
and anions is 6, and therefore the
cation–anion radius ratio is between
approximately 0.414 and 0.732.
◼ A unit cell for this crystal structure
(Figure 12.2) is generated from an FCC
◼ Cesium Chloride Structure
◼ coordination number is 8 for both
ion types. The anions are located at AX2 Crystal Structures
each of the corners of a cube, Fluorite structure UNIT CELL –TWO DIAGONALS
whereas the cube center is a single
cation.
◼ Interchange of anions with cations, and vice versa,
produces the same crystal structure. This is not a BCC
crystal structure because ions of two different kinds are
involved.
◼ Zinc Blende Structure
◼ coordination number is 4; that is,
all ions are tetrahedrally coordinated.
This is called the zinc blende, or
sphalerite, structure, after the
mineralogical term for zinc sulfide
(ZnS).
 Silicate Ceramics
Most common elements on earth are Si & O

Bond Hybridization
Bond Hybridization is possible when there is significant
covalent bonding
– hybrid electron orbitals form
– For example for SiC
• XSi = 1.8 and XC = 2.5
% ionic character = 100 {1-exp[-0.25(XSi −XC)2]} =11.5% • SiO2 (silica) polymorphic forms are quartz,
• ~ 89% covalent bonding crystobalite, & tridymite
• Both Si and C prefer sp3 hybridization • The strong Si-O bonds lead to a high melting
• Therefore, for SiC, Si atoms occupy tetrahedral sites temperature (1710ºC) for this material

Density Computations for Ceramics

Presence of cations such as Ca2+, Mg2+, & Al3+
1. maintain charge neutrality, and
4 −¿¿
2. ionically bond SiO4 to one another
Glass Structure
Layered Silicates
• Layered silicates (e.g., clays, mica,
talc)
– SiO4 tetrahedra connected together
to form 2-D plane
• A net negative charge is associated
with each (Si2O5)2-unit
• Negative charge balanced by adjacent plane rich in
positively charged cations – weak van der Waal’s forces between layers
• Kaolinite clay alternates (Si2O5 )2- layer with Al2 – planes slide easily over one another -- good lubricant
2 +¿¿
(OH ) 4 layer 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

Polymorphic Forms of Carbon

Diamond
– tetrahedral bonding of carbon Point Defects in Ceramics (i)
• hardest material known • Vacancies
• very high thermal conductivity -- vacancies exist in ceramics for both cations and anions
– large single crystals –gem stones • Interstitials
– small crystals – used to grind/cut other materials -- interstitials exist for cations
– diamond thin films -- interstitials are not normally observed for anions
• hard surface coatings –used for cutting tools, medical because anions are large relative to the interstitial sites
devices, etc.
TWO DIAGONAL LINES ZnS

Graphite – layered structure – parallel hexagonal arrays

of carbon atoms
Point Defects in Ceramics (ii)
• Frenkel Defect -- a cation vacancy-cation interstitial
pair.
• Shottky Defect -- a paired set of cation and anion usually of two different compounds.
vacancies. What is a polymer?
Poly mer
many repeat unit
NOTE: “Mer” originates from the Greek word “meros”,
which means part; the term polymer was coined to
mean “many mers.”

Imperfections in Ceramics
Ancient Polymer History
• Electroneutrality (charge balance) must be maintained
Originally many natural polymers were used
when impurities are present
- Wood – Rubber
- Cotton – Wool
- Leather – Silk
Oldest known uses of “Modern Polymers”
- Rubber balls used by Incas
- Noah used pitch (a natural polymer)
for the ark – as had all ancient mariners!
Natural Polymers
 Wool, cotton, linen, hair, skin, nails, rubber, and
flesh are all naturally occurring polymers
Ceramic Phase Diagrams  Most natural polymers are made of protein or
MgO-Al2O3 diagram: cellulose
Synthetic Polymers
 Commonly referred to as plastics – pliable, able
to be moulded
The Structure of Polymers (plastics)
 Polymers are created by the chemical bonding
of many identical units .
 These polymers are specifically made of small
units bonded into long chains.
 Carbon makes up the backbone of the molecule
Structures of Polymers/ Non-Crystalline Structures and hydrogen atoms are bonded along the
Handout No. 6 carbon backbone.
Polymers  Polymers that contain primarily carbon and
Contain thousands of molecules as repeat units (known hydrogen are classified as organic polymers.
as Mers) that are bonded into long chain interlinkage. Ex: Polypropylene and polystyrene
have a molar mass of hundreds or thousands.  Even though the basic makeup of many
The mers may polymers is carbon and hydrogen, other
1.) homopolymer – monomers of one type or elements can also be involved. Oxygen,
identical repeat units. Repeat unit is made up of one chlorine, fluorine, nitrogen, silicon,
type of compound. phosphorous and sulfur are other elements that
2.) Copolymers – the monomers are different (usually are found in the molecular makeup of polymers.
2 or more types of repeat units). Repeat unit consists
Ex: Polyvinyl chloride (PVC) contains chlorine. Bulk or Commodity Polymers
Nylon contains nitrogen. Teflon contains fluorine.
Polyester and polycarbonates contain oxygen.
 There are also some polymers that, instead of
having a carbon backbone, have a silicon or
phosphorous backbone and these are
considered inorganic polymers.
Polymer Composition
Most polymers are hydrocarbons
– i.e. made up of H and C (we also recognize Si-H
‘silicones’)
Saturated hydrocarbons

- Each carbon bonded to four other atoms

- Refer to alkanes; CnH2n+2
Unsaturated Hydrocarbons Commercially available polymers

Molecular Structures
• Covalent chain configurations and strength:
Polymers – Molecular Shape
Conformation – Molecular orientation can be changed
by rotation around the bonds
 Copolymers

- note: no bond breaking needed

Polymers – Molecular Shape

Configurations – to change must break bonds

Stereoisomerism
Tacticity
Tacticity – stereoregularity of chain

cis/trans Isomerism
Degree of Polymerization, DP Thermoplastics (80%)
DP = average number of repeat units per chain

 No cross links between chains.

 Weak attractive forces between chains broken
by warming.
 Change shape - can be remoulded.
 Weak forces reform in new shape when cold.
Thermoplastics
Degree of Polymerization  Those which soften on heating and then harden
Example: Assume that for poly(vinyl chloride the again on cooling
number-average molecular weight is 21,150, calculate  These are called thermoplastic polymers
its degree of polymerization. because they keep their plastic properties
Soln:  These polymer molecules consist of long chains
which have only weak bonds between the
chains
 The bonds between the chains are so weak that
For PVC, each repeat unit consists of two carbon atoms, they can be broken when the plastic is heated
three hydrogen atoms, and a single chlorine atom  The chains can then move around to form a
Furthermore, the atomic weights of C, H, and Cl are, different shape
respectively, 12.01, 1.01, and 35.45 g/mol. Thus, for PVC  The weak bonds reform when it is cooled and
the thermoplastic material keeps its new shape

 The bonding process.

- When thermoplastic polymers are heated they
become flexible. There are no cross-links and
the molecules can slide over each other.
- Thermosetting polymers do not soften when
heated because molecules are crosslinked Thermosets
together and remain rigid.
  Extensive cross-linking formed by covalent • This bond breaks to allow the long chains to form.
bonds. • Modifying ethene, substituting different functional
 Bonds prevent chains moving relative to each groups for hydrogen atoms produces other monomers
other. that can be polymerised to make polymers with
 What will the properties of this type of plastic different properties.
be like? • Monomers contain C=C bonds
Thermosetting • Double bond opens to (link) bond to next monomer
• Those which never soften once they have been molecule
moulded • Chain forms when same basic unit is
These are called thermosetting polymers because repeated over and over.
once set into a shape, that shape cannot be altered • Modern polymers also developed based on alkynes
• These polymer molecules consist of long chains which R-C C – R’
have many strong chemical bonds between the chains • A carbon – carbon double bond is needed in the
• The bonds between the chains are so strong that they monomer
cannot be broken when the plastic is heated • A monomer is the small molecule that makes up the
• This means that the thermosetting material always polymer
keeps its shape H H
H H high pressure/trace O2
n C C C C
catalyst
H H H H n
ethene
poly(ethene)

• The polymer is the only product

• Involves the opening out of a double bond
• The conditions of the reaction can alter the properties
of the polymer
• Reaction proceeds by a free radical mechanism
• Oxygen often used as the initiator
H
H H H H H
C C C C C C
H
H H

Kinds of Polymerization Reactions

 Addition Polymerization
 Condensation Polymerization • Conditions are high
Addition Polymerization pressure and an
• For addition polymerization to occur, the monomer oxygen initiator (to
must have a double or triple C bond. provide the initial free radical).
• This bond using its pi bond breaks to allow the long • Monomer = ethene
chains or interlinkage to form. • Polymer = poly(ethene)
• Modifying the linkage due to pi bond breakage,
substituting different functional groups for hydrogen Prediction the repeating unit
atoms produces other monomer s that can be
polymerised to make polymers with different
Example:
• When ethene is subjected to high pressure it changes
from a gas to a liquid
• Liquid ethene (still under high pressure) is heated in
the presence of a catalyst (O2), an addition reaction
takes place.
• For addition polymerization to occur, the monomer
must have a double C bond.
• This is easy, basically open out the double bond • Common condensation polymers include polyesters
H Cl H H H H (the ester linkage) and polyamides (the amide linkage as
C C C C C C in proteins).
H H H Cl H Cl • May be natural (protein, starch, cotton, wool, silk) or
chloroethene poly(chloroethene) aka synthetic (viscose, nylon, polyester)
polyvinylchloride (pvc)
Polyesters
Addition Polymers
• The OCR example here is terylene, a polymer of
• Rubber –
benzene-1,4-dicarboxylic acid and ethane-1,2- diol.
– not elastic – long chains straighten out when stretched
• The ester linkage is formed between the
and remain this way
monomers
– Susceptible to temperature changes – brittle when
Polyamides
cold and sticky when hot.
• These involve the linkage of two monomers
– Vulcanisation improved durability and elasticity of
through the amide linkage as in proteins (e.g. silk)
rubber.
Uses of polyamides
• The linear chains are cross linked using heat and sulfur
• The main use of polyesters and polyamides is as
fibres in clothing.
• Most clothing now has a degree of manufactured
fibres woven into the natural material (such as cotton).
• This gives the material more desirable characteristics,
such as stretchiness, and better washability.
• Don’t forget that proteins are also polyamides, you
must know how the linkage works with natural
Condensation Polymers polymers such as proteins.
• Condensation polymerisation uses monomers that Condensation Polymers
have two functional groups per molecule. • Nylon
• These are said to be difunctional. – Can be extruded when molten to form fibres
• Polymerisation occurs when these monomers react or sheets of strong, durable and elastic material
‘head-to-tail’ to form a new bond that will eventually – Its invention had a great impact on the textile
join the monomers together and clothing industries.
• A small molecule (often water) is eliminated Condensation Polymers
• Nylon 6 : 6
– Nylon is a linear chain containing up to 100 repeated
units.
– The name nylon 6 : 6 refers to the existence of 6
carbon atoms on each of the units

Condensation Polymers
• Involves 2 monomers that have different functional
groups. Condensation Polymers
• They also involve the elimination of water or another • PET plastic Polyethene terephthalate.
small molecule. – Soft drink bottles
• Hence the term condensation polymer. – An example of a polyester
• Monomer A + Monomer B  Polymer + small – Note the removal of H2O (condensation polymer)
molecule (normally water).
 Polymer Selection
• Due to their versatility, polymers can be produced for
almost any imagined purpose.
• A huge range of polymers exist today and are used for
many different applications.
• Their versatility has made them one of them one of
the most useful classes of substances that we rely on in
today’s society.
• This versatility can be attributed to the many different
ways that they can be modified