Materials

Dr David Harrison
School of Education and Humanities
Athrofa Addysg Uwch Gogledd Ddwyrain Cymru
North East Wales Institute of Higher Education
Wrexham, NORTH WALES
Discussion topics.
What is a metal?
What makes metals immediately recognizable?
What are the properties of metals that make them such useful materials?
To what uses are metals put? - surprisingly diverse!
What simple experiments can be carried out in the primary classroom to
distinguish metals from other materials?
INDEX:
Structure and Bonding Conductivity Lustre
Alloys Smelting Polymers and Plastics
Cotton and Linen Wool, silk and hair Nylon and Kevlar
Rubber Glass E-mail
No other materials have contributed to mankind's development over the centuries . . . except perhaps
synthetic polymers in the twentieth century. The intimate connection of metals with human development
is evident from many terms and phrases:
 the Bronze Age (circa 4000 BC onwards in Middle East),
 the Iron Age (circa 2000 BC onwards),
 a Golden Age,
 Edmund Ironside (Saxon king of England 1016),
 Copper, Tin, Silver, Golden and Platinum respectively for 9th, 10th, 25th, 50th and 70th wedding
anniversaries,
 a leaden sky and leaden footsteps,
 nickel (US 5 cent coin),
 ". . . like a lead balloon.",
 tinny, cheap or thin sounding,
 a platinum blonde,
 Golden Oldies
 " . . . a steely glint in the eye.",
 gilt-edged stocks,
 chromium plated (meaning flashy),
 a silvery voice,
 a coppery tint,
 copper-bottomed (of good quality esp. pans),
 mercurial,
 " . . . that he might hear the pudding singing in the copper." (from "A Christmas Carol" by Charles
Dickens),
 " . . . earth stood hard as iron . . ." (from the carol "In the Bleak Midwinter" by Christina Georgina
Rossetti),
 iron fist in a velvet glove, etc.,
 as bold as brass,
 brassy (shameless)
  a brazen hussy,
 to be brassed off.
that reflect some of the important properties of metals -durability, lustre, strength, hardness etc. It is no
coincidence that the cradle of the industrial revolution in Britain was the Ironbridge Gorge! (Definitely
worth a school visit!)
Pure metals are elements that comprise more than 80 (75%) of the 110 or so chemical elements,
including well known metals tin, copper, silver, iron, aluminium, sodium, mercury, uranium,
etc., and some less well known, e.g., molybdenum, tungsten, iridium, cerium, praseodymium,
etc., in fact most of the periodic table apart from the right hand corner and side. In addition to the pure
elements there are many metallic alloys- mixture of metals (and some non-metals) with metallic
properties, e.g., brass, bronze, steel, cupronickel, solder, type metal, ferrochrome,
magnalium, Misch metal, etc.
Gold was the first metal to be exploited by mankind and has always been highly valued for its ease or
working and its untarnished brilliant yellow metallic or "golden" lustre. As early as the 7th century BC it
was used in coinage. Alchemists were obsessed with discovering "philosopher's stone" or "elixir"
which would transmute base metals into gold and silver (and also prolong life indefinitely!). It is easy,
with hindsight, to ridicule what alchemists did but through their quasi-mystical experimentation they laid
some of the foundations of modern chemistry and physics.
Gold's long historical association with man arose because it is so very unreactive and occurs in nature as
the uncombined or native metal (gold is more stable as the element than in compounds). Silver also
occurs in nature uncombined and has also been used for many thousands of years. Copper very
occasionally occurs as the pure element, though more often it is combined with other elements in copper
ores, e.g., copper pyrites CuFeS2 cuprite Cu2O, malachite Cu2(OH)2(CO3) etc. However copper is
quite unreactive and is very easily recovered from its ores and this ease of recovery led man to exploit it
soon after fire was discovered. The unreactivity or noble nature of copper, silver and gold resulted in their
widespread use in coinage for thousands of years and they are collectively known as the coinage metals.
It is only in the twentieth century that the intrinsic worth of these metals in coinage has exceeded their
face value and cheaper substitutes are used, e.g., cupronickel and aluminium alloys.
Gold has another remarkable property - it is the most malleable metal known. Gold can be hammered
out into sheets of gold leaf no more than 1000 atoms thick, 1 cm3 can be hammered out to cover 3-4 m3
but more usually it is hammered out so that 1 cm3 covers 1 m2. Gold leaf is widely used in decoration and
is hammered out between the exceptionally tenacious ox intestine membrane known as gold beaters' skin.
Gold is also the most ductile of metals and can been stretched or extruded into very fine wire without
breaking. Lead and tin are amongst the least ductile of metals. The order of ductility of some familiar
metals is gold > silver > platinum > iron > copper > palladium > aluminium > zinc > tin > lead.
Malleability and ductility and other properties relating to the workability of metals are usually associated
wtth the transition metals (those forming the central block of the familiar form of the periodic table).
Top of Page
STRUCTURE and BONDING
Most metals adopt one of three structural types based on different ways of packing the metal atoms. Two
structures have the metal atoms arranged in a close packed way and differ only in the stacking of the
layers of atoms. In the third common structural type the metal atoms are not close-packed - this structural
type is adopted by metals with large atoms. For information the three types of packing are:
 cubic close packed (ccp) or face centred cubic(fcc), e.g., copper, silver and gold,
 hexagonal close packed (hcp), e.g., magnesium and zinc
 body centred cubic (bcc), e.g., sodium, potassium and iron.
Not all metals adopt these structures, that of cobalt alternates between cubic and hexagonal close packed.
Tin adopts two structures or allotropes depending on temperature. At room temperature white metallic
tin is stable but on prolonged storage below 13oC white tin turns into grey tin, a very brittle semi-
metallic form with a covalent giant structure like diamond. Napoleon's army that besieged Moscow wore
trousers and tunics fastened with shiny white tin buttons that in the severe Russian winter turned into
brittle grey tin (so called tin plague) which crumbled away - not very convenient when you want to keep
warm, you could say that Napoleon's army were caught with their trousers down and if it was cold enough
to freeze the balls off a brass monkey then pity the poor French soldiers . . . ! Tin plague was noticed by
Aristotle (384-322 BC) and Plutarch (46-120 AD). In the severe European winter of 1850 the tin organ
pipes of Zeit church in Germany were destroyed by the cold.
Whatever structure the metal adopts it is an array of metal cations and the valence electrons are free to
move or are delocalized throughout the array. The metallic bond is the 3-dimensional electrostatic
attraction of the all the metal cations for all the delocalized electrons which also serve to shield each cation
from the repulsion of neighbouring cations.
If we regard metal atoms as being like ball bearings we can understand why metals are malleable and
ductile (see later) and not brittle (unlike covalent and ionic giant structures). When subject to any
distortion the metal atoms slide past each other and the mobile electrons rearrange to ensure cation-
cation repulsions to not occur. When ionic compounds are subjected to distortion cation-cation and
anion-anion repulsions between layers of ions cause brittle cleavage. When covalent giant structures are
distorted covalent bonds are ruptured and the materials fractures unevenly - diamond may be hard but
when hit with a hammer it will shatter!.
Top of Page
CONDUCTIVITY
Metals are noted also for their thermal and electrical conductivity (lack of electrical resistance). The
high thermal conductivity makes metals cold to touch as they conduct the heat away from the fingers or
hand. Metals warm up and cool down rapidly - the metal surface loses/gains heat to/from its
surroundings which is internally conducted from/to the main body of the metal. However a shiny surface
(see later for lustre) reflects much incident infrared (heat) radiation and shiny metallic surfaces are used
for keeping heat in/out, e.g., the silvered surface in a vacuum flask and the shiny plastic survival bags
used to protect against exposure/hypothermia, and the aluminium foil which prevents your Sunday joint
from being burnt on the outside and raw in the middle. A matt metal surface heats up rapidly and also
radiates heats more effectively than a shiny surface.
Thermal conductivities J cm-1 s-1 K-1
Silver 4.16
Copper 3.86
Gold 3.02
Aluminium 2.01
Iron 0.46
Mercury 0.07
Brick 0.0063
Water 0.0055
Wood 0.0013
 thermal conductivity: silver > copper > gold > aluminium > magnesium > zinc > chromium >
iron > tin > lead,
 electrical conductivity: silver > copper > gold > aluminium > magnesium > zinc > iron > tin >
chromium > lead.
Note the close similarity in the two series both properties are related to the structure of metals. When
atoms absorb heat energy they vibrate (temperature is a measurement of molecular energy) and this
vibration is passed from one atom to the next. In metals, because the metal atoms are often close
packed together (with 12 or 14 close neighbours) the vibration or heating effect is passed rapidly through
the metal from one atom to another. In covalent and ionic compounds the atoms are not close-packed
(lower densities) and the heat energy is less easily transferred from atom to atom, also the thermal energy
is used in covalent bond vibration in covalent compounds.
Passing a current through a metal causes it to heat up because electrons are constantly and randomly
colliding with metal cations causing vibration. The lower the conductivity (or higher the resistance) or
the more obstructed is the electronic motion then the more the metal heats up and the higher the
resistance becomes leading to a further increase in the heating effect etc., thus an electric element on a fire
or cooker does not glow red instantly as it takes time for the temperature and resistance to increase. The
resistance of a tungsten filament bulb increases ten fold between room temperature and its operating
temperature.
In a light bulb the wire filament becomes very hot (white hot) and is thus made of the metal tungsten
because it has a very high melting point (3387oC). Tungsten is very reactive at this temperature so it is
necessary to exclude oxygen from inside the bulb - however in a vacuum the tungsten filament would
slowly evaporate so enough unreactive argon gas is placed in the bulb to ensure that evaporation is
suppressed at the operating temperature.
Top of Page
LUSTRE and TARNISH (CORROSION)
Another highly characteristic feature of gold and all metals is their metallic lustre which makes most
metals instantly recognizable. The surface lustre of a metal is an essential feature of their use in
decoration and ornamentation. Most metals have a characteristic silvery lustre but copper and gold have
unique salmon-pink and yellow lustres respectively. With the exceptions of gold and platinum most
metals are more or less tarnished. The tarnish may be of aesthetic beauty - the patina on antique bronze,
the beautiful green on copper roofed buildings, etc. Sometimes tarnish is synonymous with corrosion,
e.g., rust on iron and steel which is not only unsightly but is damaging and possibly dangerous, and the
black tarnish on silver, mainly silver sulphide, that spoils the brilliant silvery white lustre which makes
silver so attractive.
2Ag + H2S + 4O2 -> Ag2S(black) + H2O
The tarnish on most metals is a surface layer of oxide arising from the reaction of the metal with oxygen
in the air. In the case of aluminium, a highly reactive metal, the surface oxide layer is very tenacious and
renders aluminium quite inert to reaction.
4Al + 3O2 -> 2Al2O3
The oxide layer on aluminium can be artificially enhanced by anodizing (an electrolytic process) -
anodized aluminium can be readily coloured and painted without the need of a primer. If the surface
oxide layer of aluminium is removed the metal is much more reactive. Titanium jewellery with its
iridescent lustre relies on a special surface tarnish for its decorative value.
When iron rusts the hydrated iron oxide that forms expands and constantly peels off the surface of the
metal exposing more iron to atmospheric moisture and air.
4Fe + 3O2 + xH2O -> 2Fe2O3.xH2O(rust)
The degree to which, and rapidity with which a metal tarnishes or lustre is lost are clearly related to some
extent to reactivity. The elements below are listed in order of decreasing lustre of metal after some
exposure to air:
 lustre: gold > silver > chromium > tin > copper > zinc > magnesium > aluminium > lead > iron.
Gold and silver as we have seen already are unreactive and very lustrous. Lead although quite unreactive
is never very lustrous even when polished. Some highly reactive metals, e.g., sodium and potassium
tarnish almost instantly on exposure to air but the untarnished surface can be briefly seen when a lump of
the metal is cut with a knife.
Why are metals lustrous? Why do we see a perfect (but laterally inverted) image in a plane mirror
(silvered glass)? The lustre is intimately related to the electronic structure of a metal. Every electron can
absorb a specific quantum or packet of radiation to become excited and the quantum of radiation
absorbed depends on the energy level of the electron. "Free" electrons often absorb quanta of visible light.
In metals the outer electrons are essentially "free" electrons and their energy depends on their distance
from a nucleus; as there are countless "free" electrons of almost every possible extranuclear distance and
energy they can absorb all the visible light that falls on the metal surface thus:
 metals are completely opaque, even the thinnest gold leaf is opaque.
However an excited electron re-emits the same absorbed quantum of radiation as it becomes de-excited
and most of the radiation that is incident on a metal surface is expelled from the surface thus:
 metals are highly reflective or lustrous.
How can we protect a reactive metal from corrosion or rusting? There are four common techniques:
 painting or lacquering - the cheapest but least effective as maintenance is required. The body
of a car has a hard paint exterior but if this is damaged rusting leads to blistering under the paint
with all the tell-tale signs the motorist is familiar with - the interior of body panels is often treated
with a soft-set paints or waxes that self seal when scratched. The Forth Rail Bridge and Blackpool
 Tower need constant year on year painting as they are both exposed to corrosive sea air.
Decorative brass and copper items are often lacquered with a transparent varnish to prevent
tarnishing.
 alloying - slightly more expensive; small amounts of other metals and carbon can turn iron into
a whole range of stainless steels suitable for a wide range of applications as well as cutlery!
 electroplating - more expensive; most familiar is probably electroplated nickel silver (EPNS) as
a cheaper alternative to silver cutlery and, rather less familiar since the 1980s, the chrome
(chromium) plate trimmings on motor vehicles (bumpers, door handles, window frames,
radiator grill).
 galvanizing - an chemically cleaned iron object is briefly dipped in molten zinc (m.p. 420oC)
and is coated with a thin layer of zinc. Inspection of a freshly galvanized object (dustbin, bucket,
nail, wire netting) will reveal the obvious crystalline nature of the zinc coating. The zinc surface
gradually oxidizes so the iron surface is double protected by a layer of zinc oxide and zinc. Even
when scratched to reveal the iron surface rusting does not occur because an electrochemical
effect, arising from the two metals in contact, ensures that it is the zinc that is preferentially
oxidized. [The steel legs of off-shore oil rigs are protected from corrosion by a magnesium block
attached by a conducting cable to the steel leg - electrochemistry ensures that the magnesium is
preferentially oxidized whilst the steels remain unoxidized (reduced). The magnesium block must
be periodically renewed.]
Top of Page
ALLOYS
Alloys can be regarded as a solid solution of one metal in another. Bronze is a particularly important
alloy of copper and tin. Like copper it is corrosion resistant but it is much harder and can be used in
engineering - it is particularly useful in the manufacture of marine propellers where its corrosion
resistance is paramount but it has the additional benefit of the copper being toxic to molluscs and
barnacle growth is inhibited. Neither copper or tin are hard metals when pure so why is bronze much
harder that either component?
The atoms in most metals are close packed together in layers and these layers stacked one upon
another. When copper is squeezed or bent or beaten the layers of coppermatoms can easily slide over or
past one another hence copper is malleable and ductile. The inclusion of about 15% of larger tin atoms
disrupts the layers of copper atoms (makes the layers "rough") and prevents the layers sliding over one
another. There is also a small amount of chemical bonding between the copper and the tin which adds to
the strength.
Another important effect of alloying copper with tin is that bronze has a melting point much less than that
of pure copper (1084oC) and much higher than pure tin (232oC).
mass % mass % M.P./o
Cu Sn C
100 0 1084
90 10 1005
80 20 890
70 30 755
60 40 724
50 50 680
40 60 630
30 70 580
20 80 530
10 90 440
0 100 232
 Solder is a low melting (about 180oC) alloy of mainly tin (50%) and lead (49.5%) with antimony (0.5%)
used to join cleaned metal surfaces - a soldering flux helps by reducing any metal oxides adhering to the
surfaces to be joined. It is not possible to solder metals like aluminium which have a very tenacious oxide
surface.
Pewter comprises tin (80%) and lead (20%) and is used for decorative utensils and ornaments because it
can be carved by hand or on a lathe.
Nichrome comprises nickel (60%), iron (20%) and chromium (20%) and can be repeatedly heated to
redness and cooled without oxidation, embrittling or sagging and is used in heating elements.
Constantan comprises copper (60%) and nickel (40%) and has a resistance that does not change with
temperature.
Iconel comprises nickel (76%), chromium (15%), iron (8%) and manganese (1%) and is very inert and
widely used in food processing utensils.
Invar comprises iron (64%), nickel (35%) and carbon + manganese (1%) and has a very low expansivity
when heated.
Wood's metal (m.p. 65oC) an alloy of bismuth (4 parts), lead (2 parts), tin (1 part) and cadmium (1 part)
can be used as a heat exchange fluid and Wood's metal novelty teaspoons melted when stirring a cup of
tea!
A 3% by mass beryllium alloy with copper is hard, does not spark when struck and finds application in oil
refineries and other fires sensitive areas.
Many metals dissolve in liquid mercury to give solid alloys known as amalgams. An amalgam with silver
and tin sets rapidly into a hard mass known as dental amalgam widely used as a tooth filling. Mercury
does not amalgamate with iron and can be stored in iron flasks.
Chapter 11 (Industrial Alloys) of Bernard Moody's "Comparative Inorganic Chemistry" 3rd Edition, gives a
very thorough review of the range of metallic alloys in use today.
Top of Page
SMELTING - BRONZE & IRON AGES
Teacher Tip: opportunity here to develop cross-curricular ideas about materials, history,
and geography.
The approximately 200oC drop in melting temperature with the formation of 20% tin bronze was probably
crucial in mankind's Bronze Age development - an ordinary wood fire (approx. 950oC) will not melt pure
copper but will melt bronze so that it could be cast into a variety of shapes. How was bronze discovered?
Serendipity ensured that copper and tin ores often occur together, e.g., in Cornwall both copper ores and
tin ore (cassiterite SnO2) occur together (the British Isles were once referred to as the Cassiterides) and
accidental smelting of copper and tin ores must have occurred. Tin had been separately smelted at an
earlier date but had been found to soft to be useful. For both copper and tin ores it is sufficient to heat
them to a sufficiently high temperature in air to decompose them to the metal.
CuS + O2 -> Cu + SO2
2CuO -> Cu + O2
SnO2 -> Sn + O2
Another temperature quirk led to the Iron Age. Bronze Age man had discovered that charcoal fires
(1150oC) were hotter than simple wood fires. However iron ores are not decomposed by heating in air
alone and pure iron melts at 1535oC! But iron ores are reduced by carbon, actually by carbon monoxide, to
iron metal at charcoal fire temperature and what is more a 4% by mass mixture of carbon and iron melts
at 1150oC!
Fe2O3 + 3CO -> 2Fe + 3CO2
C + O2 -> CO2
C + CO2 -> 2CO
The same basic reactions in a modern blast furnace use iron ore and coke. A problem with cast iron from
the Iron Age forge or pig iron from the blast furnace is that the presence of the carbon makes it brittle
when cold. The carbon has a similar effect in iron as tin had in bronze - making it harder but the smaller
carbon atoms give rise to weaknesses in the atomic arrangement where fracture can occur. However iron
age man soon learned that by hammering the iron whilst still hot or forging gave a much stronger and
workable product - the hammering squeezes out and exposes the carbon and sulphur other impurities
where they oxidize in air. The hammering at the forge is not just to shape the product but also strengthen
it to give wrought iron. It was essential that some carbon was retained or the iron became less hard and
unable to keep a the sharp edge required for knives, scythes, swords, spears etc. Iron Age man also
learned to temper or harden iron by plunging it hot into water or, better still, urine! Times change - the
blacksmith and the smithy or forge were an essential feature of country-life until fifty years ago - their
memory lingers on as in Acton Smithy on the old Chester Road out of Wrexham.
Top of Page
POLYMERS & PLASTICS
Some useful Internet addresses:
All of these can be accessed from the NEWI Internet pages for Science for Education
students links page
http://www.lbl.gov/MicroWorlds/Kevlar/KevlarIntro.html - an excellent MicroWorlds resource
with many simple ideas, experiments, analogies, and demonstrations.
http://www.lexmark.com/ptc/book.html - an introduction to plastic by the Plastics Technology
Center.
http://www.umr.edu/~wlf/ - polymer chemistry hypertext, an educational resource compiled by
students, a bit heavy going.
http://www2.ncsu.edu/ncsu/pams/science_house/ctchem.html - not exactly polymers but
some recipes for some gooey colloids that can be made in the kitchen including slime, silly putty, clear
slime, glurch and cat’s meow??? Have fun!
Polymer - poly = many, mer = parts includes many natural and synthetic materials which can be
further classified as organic or carbon based and inorganic or non-carbon based and can be
regarded as being assembled from a simple repeating units held together by covalent bonds.
Natural Polymers
Organic: wool, linen, cotton, hemp, jute, wood, coal, spiders’ web, silk, starch, cellulose, proteins, latex
rubber, chicle (chewing gum), etc.
Inorganic: sand, clay, asbestos, volcanic glass (obsidian), etc.
Synthetic Polymers
Organic: polyethene, polypropene, polyvinyl chloride, perspex, polycarbonate, poly vinyl acetate, teflon,
neoprene rubber, etc.,
Inorganic: pottery, cement, concrete, silicones, etc.,
Although all the above are polymeric materials the term polymer usually refers to the synthetic organic
polymers often referred to as plastics or synthetic fibres (or synthetics). Many are household
names, e.g., nylon, terylene, teflon, rayon, acrylic, polyester, perspex, polystyrene, etc., and
most are derived from natural petroleum.
All polymers are assembled from repeating units. The repeating unit may be derived from one or more
monomers.
There are many ways of classifying these synthetic organic polymers as indicated below:
thermoplastic and thermosetting - the former soften and melt on heating and can be moulded, e.g.,
polyethene, the latter decompose on heating and must be shaped at manufacture, e.g., bakelite.
addition and condensation - the former are made from the simple addition of monomers, e.g.,
polyethene from the addition of ethene, the latter are usually synthesized from two different monomers
with the elimination of biproduct, e.g., nylon 6-6 from hexandioyl chloride and 1,6-diaminohexane with
elimination of HCl.
homopolymer and copolymer - the former are assembled from one repeating unit, e.g., propene in
polypropene, the latter are based on two different repeat units, e.g., nylon.
atactic and isotactic (also syndiotactic) - the former has chemical groups attached to the polymer
chain randomly on either side of the carbon chain, the latter has the chemical groups attached to the same
side of the carbon chain, e.g., atactic and isotactic polypropene, syndiotactic polymers have the groups
alternately on oppostite sides of the chain.
crystalline and amorphous - the latter are stronger and have the polymers chains stacked together in a
more or less ordered form, e.g., high density polyethene (HDPE), the former are of lower strength and
have the polymer chains randomly arranged because of branching or bulky side groups, e.g., low density
polyethene (LDPE) or atactic polypropene.
linear (or straight chain), branched and cross-linked - the former have long chains of carbon atoms
only, e.g., natural latex rubber, branched chain polymers as the name indicates are branched, cross-linked
polymers have polymer chains joined together by other atoms, e.g., vulcanized rubber.
Teacher Tips
Use paper clips to act as monomers and these can be linked together to give chains, branched chains
and cross-linked chains. Coloured paper clips could be used to model homo- and co-polymers.
Use uncooked spagetti to model a crystalline polymers -many sticks of spagetti lie side by side in an
ordered fashion; cooked spagetti is a model for an amorphous polymer.
Top of Page
The Structure of Polymers - Polythene
Polythene is a polymer formed by the polymerization of ethene. Its formula can be variously
represented as CnH2n+2 (n = large integer 100 - 200 000) or CH3-(-CH2-)n-CH3 or -(-CH2-CH2-)-n etc.,
all of which amount to the same thing, that is long chains of CH2 groups though at the ends of the chains
there must be CH3 groups to ensure that each carbon atom always forms four bonds. The value of n
in the above formula is variable in polyethene from hundreds to hundreds of thousands and the average
value of n is a measure of the average chain length - because of this variation polyethene is not, strictly
speaking, a pure compound as the molecules are not all the same it is better to call it a mixture of
hydrocarbons.
The simplest hydrocarbon is methane CH4 (n=1) which is familiar as natural gas; bottled heating and
cooking "Calor" gas is propane CH3CH2CH3 (n=3); camping gas and lighter fuel is mainly butane
CH3CH2CH2CH3 (n=4); petrol is mainly CH3CH2CH2CH2CH2CH2CH2CH3 or octane; paraffin wax
for candles has on average twenty carbon atoms in a chain, i.e., typically C20H42; the waxes found in shoe
polish and vaseline have upto 70 carbon atoms in the chain.
The chains are not straight chains but in fact zig-zag chains - the term straight refers to the fact that they
are not branched! The zig-zag nature of the chain arises because when we look down a carbon-carbon
bond the atoms attached to adjacent carbon atoms should always be "staggered" rather than "eclipsed" -
this is known as the staggered conformation and is more stable.
Notice also that as the chain of carbon atoms gets longer the materials change from gases to volatile
liquids to oils to waxes to solid plastics. The only bonds in these compounds are covalent bonds
between the atoms in the molecule (C-C and C-H bonds which are strong) but there are no bonds
between the molecules. So what is holding the molecules together? Why are all hydrocarbons not
gases like methane?
There are very weak intermolecular forces called London or dispersion forces that give rise to
van der Waals interactions between molecules. These forces of attraction between molecules arise
because electrons in the covalent bonds are always in motion and at any instant a pair of electrons
may not be equally shared between the two atoms of a covalent bond, i.e., there will be instantaneous
bond polarization Cd +-Hd -. This bond polarization induces bond polarization in neighbouring
molecules leading to very weak electrostatic attraction bewteen molecules. In methane however
the van der Waals forces are to small to overcome the thermal motion of the molecules due to their kinetic
energy at room temperature and methane is a gas. As the temperature is lowered and the thermal kinetic
energy gets less then methane eventually liquefies and at very low temperatures freezes.
Although molecular size increases in longer hydrocarbon chains, the van der Waals forces do not increase
and the thermal energy remains the same as for methane at a given temperature. But, because the
molecules are heavier, the speed at which they move becomes less (kinetic energy is 1/2mv 2 m = mass, v =
speed) and are thus less likely to be able to escape from the weak van der Waals attraction of another
molecule. Also longer molecules have more van der Waals contacts as shown below.
The lecture diagram showed sections of zig-zag polythene stacked together in a highly idealized manner.
In practice polymer chains are never stacked as regularly as shown above for several reasons:
 the polymer chains are very flexible and can be twisted into other
orientations,

 the chains tend to form loose spirals or coils,

 the chains may be branched,

 not all polymers are ordered or crystalline.

Low density polythene LDPE is obtained by polymerization of ethene at high pressure (1000
atmospheres) and high temperature (200° C) which leads to a waxy solid in which the polymers chains
have irregular branches and cannot pack together in an ordered way shown above - there are still van
der Waals attractions between the chains but these are of random orientation. The result is that LDPE is
an open polymer of low density and little mechanical strength and rather a tangled mess at the molecular
level.
Polythene can also be prepared catalytically by use of Ziegler-Natta catalysts at lower pressures (1-10
atmospheres) and temperatures (50-100° C). The catalyst is a metal compound and the polymerization
occurs at the metal atom in a conveyor belt fashion which gives rise to a regular non-branched chain
polymer which is highly ordered or crystalline with regular van der Waals attractions between chains and
is known as high density polyethene HDPE. HDPE is tough and strong and the ordered structure
means that it has higher density.
HDPE and LDPE can be distinguished by their transparency: LDPE is fairly transparent (sandwich
bagsand bread bags) whereas HDPE is whitish and at best only translucent (supermarket carriers &
plastic milk bottles).
Even in HDPE the ordering of the polymer chains is not complete - there are definite regions of the
polymer where the chains are packed in an orderly fashion and these regions are called crystallites. The
number of crystallites determines the crystallinity of the polymer. In between the crystallites are
areas where the polymer chains are more randomly arranged. The crystallites act rather like the cross-
links in a thermosetting polymer and by holding the polymer chains tightly together give HDPE the
strength and toughness that are lacking in LDPE. Although van der Waals attractions are weak (5-20 kJ
mol-1) when concentrated in an orderly fashion in the crystallites they can give a polymer strength.
Polythene is very familiar as the plastic of plastic carrier bags from supermarkets which are made of thin
HDPE. The way HDPE is manufactured and its structure ensures that most the polymer chains are
arranged so as to give the internal structure a fibrous nature or grain. As with any "grained" material the
strength varies according to whether tension is applied across or with the grain, this can be demonstrated
with a supermarket carrier bag.
Cut out two similar large squares (6" x 6") from a plastic carrier bag noting carefully which edges
correspond to the top and bottom and side of the bag. Make a small cut in one edge of each square - the
top edge of one square and the side edge of the other square.
Grasp each square in turn firmly with both hands and pull gently so as to tear each square starting at the
small cut. Repeat the experiment several times to convince yourself (or not as the case may be) that the
polymer does not tear as easily in both directions. As supermarkets bags become thinner, for reasons of
economy, this experiment becomes less reliable but you should find that the bag tears more easily
from top to bottom than from side to side. This is because the polymer chains are aligned from top to
bottom and tearing in this direction or with the grain involves breaking mainly weak van der Waals
attractions. Tearing from side to side or against the grain must involve breaking not only van der Waals
attractions but some covalent bonds as well which requires more energy and is thus more difficult. The
bags are made in this away because most of the strain is in the vertical direction which parallel to the
grain and would tend to pull the bag apart perpendicular to the grain.
Next cut out a vertical strip from your bag. It should be about 1" or 2.5 cm and 6" or 15 cm long. Grab
hold of each end of the strip and pull gently but steadily - observe and describe what happens and try to
monitor changes in stress in the plastic as you increase the strain. If necessary repeat the experiment
several times to ensure that it is reproduceable.
When you start to pull on the strip nothing happens at first except a little stretching but then as you
increase the applied strain one or more "necks" form in the strip and as you continue to increase the
strain the necks get longer as material appears to "flow" into the necks from the taut regions, either side of
the neck, which get smaller. Eventually the neck grows to the whole length and the polymer becomes
stiffer and ridged - it is difficult to stretch at this stage and eventually, as you increase the strain beyosd a
certain point, the strip snaps.
We can explain what is observed by considering the changes on a molecular scale. The individual polymer
chains are held together by van der Waals forces so that the chains are parallel within crystallites.
However, although the chains are parallel, they are not straight but are randomly coiled. When tension is
applied there is a tendency for the uncoiling to occur which results in a highly aligned molecular structure
-this occurs as the "necks" are formed in the strip of plastic. The uncoiling and alignment continues until
all the molecules are highly aligned and at this stage the strip has become noticeably more rigid and
ridged reflecting the highly organized linear structure. The uncoiling and alignment can occur because van
der Waals attractions are weak and easily broken and reformed. Eventually when enough strain is applied
the highly aligned molecules slide past each other, overcoming the van der Waals attractions, and the
polymer breaks.
 The high level of strain required to break the polymer explains why it is so difficult to tear open a bag of
frozen peas - you have to tug and pull very hard and then suddenly it rips open and you’ve got peas all
over the kitchen floor! It is much easier to open the bag if the manufacturer provides a weakness or flaw
into the packaging which allows you to concentrate your applied tension in one area.
Top of Page
Change of State
A convenient way of identifying a pure solid organic compound is by the determination of its melting
point, e.g., pure benzoic acid crystals C6H5COOH have a melting point of 122° C.
HDPE is an organic compound but differs from other organic compounds in two ways:
i. it is only partly crystalline or ordered unlike benzoic acid crystals
which are almost perfectly ordered,
ii. it is not a single compound but is a mixture of compounds of
formula CnH2n+2 where n is large and variable, i.e., it is not a pure
substance.
HDPE thus does not have a sharp melting point. When we heat it up slowly nothing happens for a while then
there comes a temperature at which it starts to gradually change from a hard solid to a treacle like
substance. The temperature at which this starts is known as the glass transition temperature, so
called because glass behaves in a similar way - it starts to soften and flow but does not melt to a runny
liquid.
Chewing gum, either based on natural chicle from the sapodilla tree or synthetic based on poly(vinyl
acetate), is a relatively brittle material at room temperature - a stick of gum straight from the packet is
not chewable. However most chewing gum has a glass transition temperature of around 25-30° C (pva
gum 28° C) and in the mouth, temperature 37° C, it becomes the soft chewy material we are familiar with.
The glass transition temperature varies from polymer to polymer and depends on:
(i) the average chain length,
(ii) the rigidity of the polymer chains,
(iii) the strength and nature of interactions between chains,
(iv) the degree of crystallinity.
When polymers soften (we should not use the word melt) they do not become runny liquids - why not? Ice
melts to become water! The reason is that when polymers soften each molecule cannot behave
independently, like a small molecule, because they are all entangled and there are still van der Waals
attractions, although these are random rather than ordered. To use the cooked spagetti analogy again, the
softened polymer chains are like a tangled mass of cooked spagetti - try to move one string of spagetti on
its own, it cannot be done! In a true liquid (a molten solid) each individual molecule can behave
independently - this is not possible in a softened polymer. The glass transition temperature marks a
boundary between little or no molecular movement (solid) and restricted molecular movement (treacle-
like).
Cotton has a glass transition temperature of 225° C so cotton fabrics keep their shape because the cotton
molecules cannot move at room temperature. Cotton is a carbohydrate polymer of glucose which contains
lots of hydroxy groups, -OH, and these can hydrogen bond (another story for another lecture) to -OH
groups in another polymer chain. The inter-chain hydrogen bonding is much stronger than van der Waals
attractions in polyethene so cotton is a much tougher material than polyethene and can form strong fibres
which can be formed into threads, which cannot be done for polyethene. The high glass transition
temperature reflects the strength of the forces between the polymer chains.
However cotton absorbs water which, because it contains -OH groups, will also hydrogen bond to the
polymer - one reason why undergarments are cotton rich is because they are absorbent. Water acts as a
plasticizer or lubricant between the chains allowing them to move more freely and lowers the glass
transition temperature to 20° C. Cotton shirts and blouses thus crease most where they absorb most
moisture and are under most pressure - inside the elbows, under the arm pits, where they are tucked into
trousers, etc. Where they are not subject moisture or pressure they remain quite flat and uncreased. The
lubricating power of water is used when we use a steam iron to press our cotton shirts or blouses - the
high temperature speeds up molecular motion and make the pressing process more rapid, it could be
done at 20° C but it would be a very slow job!
PVC (polyvinyl chloride) is a rigid polymer that is difficult to process for most applications but we are all
familiar with pvc in clingfilm, shower curtains, waterproof clothing, pvc wellies, synthetic upholstery and
all these applications rely on substantial amounts (upto 50%) of plasticizers. The plasticizers in
clingfilm had a bad press a few years ago when people worried about migration from the film to the food.
A typical plasticizer is dibutyl phthalate - it is responsible for the oily film that condenses on the inside of
the windscreen of a new car as it is released from the vinyl upholstery and dashboard and is also
responsible for the smell of a new car. Of course when you have your new double-glazing installed you
want only the best - UPVC frames - which should be strong and rigid and so are made from Unplasticized
PVC.
Top of Page
COTTON and LINEN
The nature of cotton was briefly discussed in the last lecture. Cotton and linen are both natural
cellulose polymers based on glucose as the repeating unit. They both form strong fibres that can be
woven into threads. Polyethene does not form strong fibres and cannot be woven into threads. This
difference in behaviour can be explained by the different nature of the forces of intermolecular
attraction between the polymer chains. In polyethene the only forces between the polymer chains are
van der Waals attractions.
In polymers based on cellulose there are, in addition to van der Waals attractions (these are always
present), hydrogen bonding interactions. Hydrogen bonds are about five times stronger than van der
Waals attractions but only about one tenth of the strength of a covalent bond.
van der waals attraction 5-10 kJ mol-1
hydrogen bond 25-50 kJ mol-1
covalent bond 250-500 kJ mol-1
The hydrogen bond occurs between hydrogen atoms that are themselves attached to oxygen or nitrogen
and oxygen or nitrogen atoms in another molecule. -OH groups are known as hydroxyl groups and N-
H groups as amino groups or, in some cases, amido groups.
Hydrogen bonding arises because oxygen and nitrogen are very electronegative elements, i.e., they
strongly attract electrons towards themselves in compounds, and as a result O-H and N-H bonds are
very polar. The electrostatic force of attraction of the positive hydrogen end of an O-H or N-H
bond for another electronegative oxygen or nitrogen atom in another molecule results in the hydrogen
bond. Hydrogen bonds are about twice as long as a normal covalent bond, e.g., O-H or N-H typically 90
to 100 pm and O----H and N----H 180-200 pm [pm = picometre or 10-12 m].
Don’t try to remember the structure of cellulose! Just remember that it is a polymer of glucose, which
is a carbohydrate, and has lots of hydroxyl groups -OH that can hydrogen bond to oxygen
atoms in other polymer chains giving rise to strong intermolecular attractions leading to a strong
polymer that can be woven into threads.
Top of Page
WOOL, SILK and HAIR
Other natural fibres that contain hydrogen bonded polymer chains are wool and hair, examples of
animal fibres. These are however a different sort of polymer as the repeating groups are amino acids
and this sort of polymer is a protein which is a polyamide known as a polypeptide. The term
polypeptide is reserved for polymers containing the amide link derived from amino acids.
As the lecture diagram showed, there is scope for hydrogen bonding between amido groups. There are,
however, many different amino acids so the protein chains in animal fibres can have a variety of different
repeating units made up of different combinations of amino acids. The different repeating units leads to
different possibilities in the secondary structure of the animal fibre because of different hydrogen
bonding possibilities not only between polymer chains but within the polymer chain. a -Keratin the
protein of wool, human hair, nails and feathers has the individual polymer chains coiled into a right
handed helix, or a -helix, held together by hydrogen bonds. The helical chains of wool and hair are
then coiled about one another, held together by further hydrogen bonds, to form a superhelix which
accounts for the thread-like nature of these proteins.
Another protein known as silk fibroin has different protein chains hydrogen-bonded together to give a
puckered layer structure known as a b -pleated sheet. (The hydrogen bonding pattern is very similar to
the pattern of van der Waals forces between zig-zag chains of polyethene.)
However in the case of wool or hair this is not the complete story. One of the amino acids that make up
the protein of hair and wool is cysteine HSCH2C(NH2)CHCOOH. When two cysteine molecules in
adjacent protein chains are close together they react together, or are oxidized, to give cystine which
contains an S-S bond that holds the protein chains by covalent bonds, the protein or polymer chain
is crosslinked.
The crosslinks that hold the chains together give a very durable fibre that retains its shape. The
crosslinks survive stretching and wool is springy and when when pulled or stretched returns
immediately to shape when released. The curliness in hair is due to the S-S bonds in cystine which hold
the hair protein chains together. The S-S bonds can be removed by reducing agents. In the reduced form
the hair can be brushed, combed, rollered and held into a new style. The hair can then be re-oxidized to
form new S-S bonds which then retain the new style. This is the basis of the permanent wave or perm
of the ladies’ hairdressers - and the process is responsible for some of the stranger odours found in
those establishments! A sulphur crosslink is also found in vulcanized rubber (see below).
Top of Page
SYNTHETIC POLYAMIDES - NYLON and KEVLAR
Synthetic polymers that contain the amide link are known as polyamides and have the same
repeating units throughout unlike the natural proteins. Nylon and Kevlar are examples of polyamides.
Like proteins the polymer chains are held together by hydrogen bonds but they do not have the
complex hydrogen bonding within the chains that give rise to the complex spiral structure of some
proteins. Nylon was discovered in 1935 by an American Wallace Carothers (1996-1937) who worked in
the Research Division of the chemical company Du Pont - however despite his discovery he was obsessed
with self-failure and committed suicide before the large scale manufacture of nylon (after New York and
London) began in the U.S. during WW2.
Nylon 6-6 or nylon 66 is a condensation copolymer made from hexandioyl (adipyl) chlorideand
1,6-diaminohexane. In the laboratory last week you saw the preparation of nylon 68 in the nylon
rope trick - this used octandioyl (sebacoyl) chloride as one of the monomers (two more carbon atoms in
one of the monomers). In the reaction hydrogen chloride (hydrochloric acid gas) is formed or "condensed"
from the reactants.
Another type of nylon called nylon 6 is a homopolymer made from only one monomer called
caprolactam. Caprolactam, a ring amide, is heated with water to give a chain compound 6-
aminohexanoicacid which on strong heating forms the condensation polymer (releasing water)
nylon 6. In caprolactam the amide groups are formed intramolecularly to form rings whereas in nylon 6
the amide links are formed intermolecularly to give long chains.
In addition to van der Waals forces and hydrogen bonding in nylon there are dipole-dipole attractions
between chains. These are electrostatic attractions between polar bonds that are similar to, but
weaker than, hydrogen bonds. In addition to side to side bonding between chains by hydrogen bonding
the additional attractions can give rise to bonds to other polymer chains above and below a polymer chain.
As a result of all three inter-chain attractions nylon is extremely strong and tough. Thin extruded
nylon wires, like fishing line, can withstand surprisingly high tensional stress. Nylon can be used to
prepare cogs for motors and gears because it is very hard wearing and abrasion resistant, it is lighter and
more durable than metal cogs and requires less lubrication. Nylon, because it is so strong, can be spun
into very fine threads suitable for weaving into cloth. In the 1960s there was a vogue for nylon shirts
(BriNylon was the British product) -they were drip-dry and required little or no ironing but they did not
keep their shape like cotton and were non-absorbent and "sweaty" to wear. Nylon shirts were however
very hard wearing and did not shrink or stretch - one snag was that the cotton stitching wore out long
before nylon material. What gave you street cred in 1960s would definitely make you a nerd today! Nylon
curtains were a failure too, as nylon is degraded by ultra-violet light in sunlight.
Kevlar is another type of polyamide called an aramid (from aromatic amide) prepared from the
reaction of 1,4-diaminobenzene and 1,4-benzenedicarboxylic acid. Any compound containing the ring of
carbon atoms found in benzeneis said to be aromatic - the name arises because many simple benzene
compounds have very characterisitic odours.
The benzene rings are planar and ensure that the polymer chain is almost flat. The flat nature of the
Kevlar chains means that they hydrogen bond together to give sheets and these sheets are stacked one
upon another and are held together by dipole-dipole attractions. The highly organized or crystalline
nature of Kevlar has been demonstrated by a special form of X-ray microscopy called XANES and
contributes to its enormous strength.
Kevlar cables are many times stronger than steel cables and much lighter and corrosion resistant and find
application in marine engineering. Bullet proof vests, windsurfing sails that can stand 60 mph gales
without tearing, skis, golf clubs, aircraft parts, gaskets and brake linings are all manufactured from
Kevlar. The comparative strengths of some polymers is given below.
Kevlar 20-30 gram/denier
Rayon 1-2
Nylon 66 3-10
Nomex 4-5.5
Nomex is very similar to Kevlar but the amide groups are attached to the benzene rings in a different
orientation.
Top of Page
RUBBERS or ELASTOMERS
Natural rubber is a unique polymer and was exploited by South American Indians to make waterproof
clothing and footwear long ago. Columbus in 1493 recorded that Indians played with a ball made from a
tree gum ". . . which tho’ heavy would fly and bound better than those fill’d with Wind in Spain." [J.
Chemical Education, 1990]. Rubber arrived in Europe in 1735 as "caoutchouc" from the Indian
word "caa" (wood) and "o-chu" (to flow or weep). Joseph Priestley coined the word India Rubber in
1770 when he found that it erased pencil marks on paper better than using breadcrumbs. Charles de la
Condamine observed that Amazon people poured rubber tree sap on their feet to make waterproof boots
- instant wellies! He did not record whether they were also practised at instant birth control! In 1823
Charles Mackintosh made a rubber solution that enabled him to make a sandwich of rubber between
two layers of cloth and made the first mackintoshes.
Rubber is derived from the sap or latex from the rubber tree Hevea braziliensis. The sap is a
suspension of a natural polymer in water which, on on acidification, coagulates and is made into sheets of
crêpe rubber, a tacky elastic waterproof material. Michael Faraday found that rubber was made up of
C5H8 units or cis-isoprene units . Gutta percha is another natural polymer of trans-isoprene which
differs in the arrangement of atoms about the double bond - it is hard and horn-like and was used to make
golf balls.
The polymer chains in rubber, because of the shape of the repeat unit and its double bond, are strongly
coiled and held as coils by van der Waals attractions. When pulled the coils straighten out to
become extended chains and the rubber stretches. When the tension is removed the rubber chains
return to their orginal coiled arrangement. The stretched coils do not form new van der Waals attractions,
and hence retain their stretched shape, because the rubber polymer chains are not packed tightly together
because of the side chain (CH3) attached to the double bond. Rubber is an example of an elastomer.
Natural rubber is a thermoplastic and in hot weather becomes soft and sticky and in cold weather hard
and brittle. In 1839 the American Charles Goodyear made the accidental discovery that the addition of
sulphur to natural made a much more useful polymer that was stable to heat and cold and no longer
soluble in organic solvents but still rubbery. He had invented the process of vulcanization.
When natural rubber is heated with sulphur a reaction occurs between some of the double bonds in
neighbouring rubber chains and the sulphur to give sulphur cross-links between the chains. This
gives rise to changes Goodyear noticed. The more sulphur is added the greater degree of cross-linking
occurs - elastic bands are soft and very stretchy and have only small amount of cross-linking. Tyres are
made of extensively cross-linked rubber which is quite hard and bouncy rather than elastic. 1% cross-
linking actually improves the elasticity of rubber as it prevents molecular slippage. The situation is very
similar to that in wool described earlier.
Much rubber is now synthetic including neoprene, butyl rubber (pond and landfill linings),
polybutadiene (modern golf balls) and SBR (Styrene Butadiene Rubber) for modern tyres, chloroprene
(like ordinary rubber except CH3 group replaced by Cl) which has a greater resistance to oils, heat and
oxygen, BUNA S or GRS which is a copolymer rubber of butadiene and styrene.
CONTACT LENSES
For many years contact lenses were made of glass which had to be individually ground, were "hard" on
the cornea, and inflexible. About 50 years ago "perspex" contact lenses were introduced which was more
easily machined than glass, was less prone to chip or break if accidentally dropped, and were
physiologically harmless to the eye. However it was stil "hard" on the eye - what was wanted was a flexible
contact lens.
Perspex is an addition polymer of methyl methacrylate or methyl2-methylpropenoate and is
known as poly(methyl methacrylate) or PMMA. By replacing one of the methyl groups with an
hydroxyethyl group to give 2-hydroxyethylmethacrylate a new polymer can be prepared which has all
the desireable properties of PMMA but has some additional useful features. The presence of the hydroxyl
group allows the polymer to absorb water by hydrogen bonding which lowers the glass transition
temperature and it becomes a clear flexible gel - the absorbed water is a plasticizer. Water also
effectively lubricates the contact surface between the cornea, the eyelid and the contact lens and the
contact lenses are much less irritating.This new polymer is known as a hydrogel and finds application
not only as a contact lens but also in lens replacement after cataract removal.
Top of Page
POLY(ETHYLENE TEREPHTHALATE) (PET) or TERYLENE (POLYESTERS)
This polymer is the most notable example of a polyester which contains the ester linkage and is a
condensation polymer made by elimination of water between molecules of 1,2-ethanediol (ethylene glycol
- antifreeze) and terephthalic acid (benzene-1,4-dicarboxylic acid).
PET can be manufactured into a wide variety of different forms - as thin films it is the base of magnetic
tape, as thicker film it is used for "boil-in-bag" food packaging, a thicker layer is used for soft-drink bottles
and oven ready trays for convenience foods, and in the fibrous form it can be woven into polyester
materials, e.g., TeryleneTM, CrimpleneTM or DacronTM.
A look at the structure of PET shows that there are no hydrogen atoms attached to the oxygen atoms so
there is no possibility of hydrogen bonding between polymer chains. The inter-chain attractions in
polyesters are of van der Waals and dipole-dipole nature between the C=O or carbonyl groups.
Polyester is stronger than polyethene (van der Waals only) but less strong than nylon (van der Waals +
hydrogen bonds + dipole-dipole).
BIOPOL
Biopol (ICI 1980s) is a polyester copolymer of 3-hydroxypentanoic acid and hydroxybutanoic acid
that is slowly and harmlessly dissolved in the body so it is used in sutures (stitches). The interesting
feature of this polymer is that it is produced by fermentation. A bacterium, Alcaligenes eutrophus, is
cultured in a medium containing glucose, pentanoic acid etc. As the bacteria grow they manufacture the
polymer to store as a food reserve (much as we store fat) and by the end of fermentation the dried bacteria
may contain 70% or more by mass of the polymer. The polymer can be made from entirely natural
sustainable materials (plant sugars) and is also biodegradeable as the ester bonds are slowly attacked
by water (hydrolysed) and the products are gradually oxidized in the environment to carbon dioxide and
water. In May 1997 the Cooperative Bank announced that its bank cards were to be made of Biopol to
emphasise its credentials as the the U.K.’s "green" bank.
GLASS
Pliny the Elder recorded that Phoenician sailors came ashore and, not finding any local materials
suitable for supporting their cooking pots above the sandy shore, used lumps of of trona (natural soda
or sodium carbonate) that formed part of their ship’s cargo. As the trona was heated in the fire it
combined with the sand to give a material that flowed. This story may not be entirely accurate but points
to the fact that glass as a man-made material has a long history and some of the oldest dated Middle
Eastern pieces are over 4000 years old; a deep blue charm is estimated to date from 7000 BC. Egyptians
and Romans fashioned a wide range of intricate and coloured glass objects. A highly developed glass
industry in Syria in 1500 BC. In medieval times the centre of the glass blowing expertise was Venice
(1200-1600 AD).
The serendipitous preparation of glass by the Phoenician sailors is basically the same as that used today. A
mixture of purified sand is heated with sodium and calcium carbonate together with some sodium
sulphate. The gases evolved help to stir the mixture. The addition of calcium is necessary to make the
glass insoluble in water - simple sodium glass is water soluble to give a very viscous liquid known as
water-glass (used as an egg preservative in WW2). For those who like the chemistry:
Na2CO3 + SiO2 -> Na2SiO3 + CO2
CaCO3 + SiO2 -> CaSiO3 + CO2
Na2SO4 + SiO2 -> Na2SiO3 + SO3
Glass made as above is known as soda-glass. Replacement of sodium with some pstassium give a harder
glass that is familiar as window and bottle glass. The molten glass is made by a continuous process and is
floated on a bath of pure molten tin, with which it does not mix, and cooled to give flat smooth sheets. The
scale of production is enormous - in 1939/40 a glass melting plant poured out a 51" wide sheet of glass
without interruption for 600 days - each day 3.25 miles of glass poured from the plant which is 46,000
tons or 42,100,000 square feet!!!
Common glass is sodium (+ potassium) calcium metasilicate but by replacing the metal ions (Na,K,Ca) by
other metal ions (Pb,Ba,Fe,Co) and by replacing the silicate (SiO3) with borate (BO3) or phosphate (PO3) a
wide variety of different glasses can be made.
Write down what you consider to be the most important advantages and disadvantages of
glass.
Let us look at some of the features you have listed. Hopefully you have placed transparency as one of
the most important advantages of glass.
Transparency - the ability to transmit (conduct) visible light without distortion. What other
common materials are transparent? most liquids and some plastics (perspex, polycarbonate). Note
that coloured glass is transparent but only to selective wavelengths of light. What have many of these
materials in common? They have non-ordered structures - they all have the "liquid" structure, i.e.,
molecules in close contact but free to move. Glass can be considered as a very viscous liquid. Does glass
flow like a liquid? Yes it does! When stained glass windows at Chartres Cathedral were restored it was
found that many pieces of glass were much thicker at the bottom than at the top because the 500 or 600
year old glass has flowed under the influence of gravity. Glass, like many polymers, does not melt - it
softens into a treacly liquid above the glass transition temperature (see polymer notes).
Any of you who use a dishwasher may have noticed that glass items that are regularly washed in a
dishwasher become cloudy or, in extremes case, opaque. This devitrification occurs because certain
components of dishwasher detergents chemically scour the glass surface and induce the growth of tiny
crystals which continue to grow (much like clear honey eventually crystallizes) and render the glass
opaque. The devitrification extends into the glass and cannot be removed by polishing.
Top of Page
Structure and Bonding
The structure of glass can be regarded as a mixture of an ionic compound (containing cations and
anions) and a covalent polymer(containing long branched chain molecules). The basic structure
comprises long branched polysilicate chains that are sometimes known as network formers. The chains
are tangled and branched and even when molten the chains are not free to move and molten glass is
viscous. The silicon atoms can be, partly or wholly replaced by, e.g., boron in borosilicate glass or
PyrexTM or phosphorus in crown glass (optical glass). The lecture diagram showed a tiny fragment of a
polysilicate chain. Each silicon is covalently bonded to four oxygen atoms and each oxygen can
either form two covalent bonds to silicon OR forms one covalent bond and carries a negative
charge.
In order to balance the accumulated negative charge on the silicate chains there are metal cations that
randomly occupy suitably sized cavities in the silicate network. The bonding between the cations and the
chain anions is ionic.
When simple glass is subject to stress - dropped on to a hard surface or hit with a hammer - it shatters
readily because it is brittle. This brittle nature arises, in part, from the ionic nature of glass - ionic
compounds are usually brittle, e.g., a large crystal of rock salt will shatter is struck with a hammer.
However the way in which glass breaks is different to that of ionic compounds. Ionic compounds contain
highly regular arrays of ions and split or cleave cleanly between layers or rows of ions - ionic compounds
display good cleavage. Glass does not cleave - it fractures - or breaks randomly to give curved
(conchoidal) surfaces with sharp edges. The random fracture arises, in part, because of the lack of order
on the molecular scale.
Why does glass sometimes shatter when heated suddenly? There are three properties of soda-glass that
lead it to shatter:
 expands significantly when heated,

 is a poor conductor of heat,

 the structure contains voids.

When hot water is poured into a cold glass vessel the inner wall of the glass in contact with the hot water
expands. However because glass is a poor conductor of heat the outer walls remain cool and do not
expand but remain in contact with the expanded inner surface. The temperature difference thus sets up
strain in the glass which may lead to cracking or shattering. Thin walled tumblers are much less likely to
crack as a result of thermal stress than are thick walled tumblers. The expansion of glass is
concentrated around voids in the structure of glass. An article manufactured out of thick glass needs
careful annealing (heat treatment) and slow cooling to remove strain - the 20 ton glass mirror used to
manufacture the 200" reflecting mirror of the Mount Palomar telescope required one year’s cooling!
PyrexTM or borosilicate glass contains about 12% boric oxide replacing some silicate and contains much
less sodium and more aluminium. The resultant glass contains more branching and cross-links and fewer
voids, expands very little when heated, is not subject to the thermal stresses of common glass and is
widely used for oven-to-table ware. More sophisticated glasses can be used to manufacture pans that can
be placed directly onto a gas flame or red hot electric cooker ring.
Ultra low expansion glass VycorTM is made by moulding a vessel from glass and then leaching out the
metal oxide with strong acid to leave only the silica network. The vessel is then baked at high temperature
wherupon it fuses and shrinks to give a translucent glass resembling quartz that can be plunged from red-
heat into ice-cold water without shattering.
Glass can also easily shatter as a result of impact and in many situtations this is highly undesireable. Car
windscreens are regularly hit by flying grit and insects - a cockchafer beetle hitting a windscreen at 40
mph packs quite a punch! It is essential that a windscreen such be able to withstand such impacts and, if it
does fail, that it does so safely. The glass windscreen is carefully annealed or tempered during
manufacture to strengthen it and also incorporates a polymer interleaving which prevents the glass shards
from dispersing if the windscreen shatters. The dis-benefit is that if the windscreen shatters whilst the car
is in motion the driver cannot see a thing through the crazed glass until he/she is able to break a hole in
the windscreen.
Specially toughened glass AmourplateTM and HerculiteTM are used in the construction industry (glass
doors etc.) and are manufacture to shape, then heated to softening point and chilled suddenly to leave the
surface of the glass under a good deal of compressive tension - such glass is four or more times stronger
than ordinary glass but cannnot be machined further. Glass can also be reinforced with steel mesh to give
security glass (burglar proof).
What colour is ordinary glass? Look through a section of the base of a milk bottle and you’ll see that it is
perceptibly green. The old ink-bottle, shown to you in the lecture, is more distinctly green. The green
colour is due to ferrous Fe2+ ions in the glass which come from impurities in the sand - mainly iron oxide
(Fe3+)(O2-)3 (rust). The Fe3+ ions are reduced to Fe2+ during the manufacture of the glass. However by
using purified sand the green colour is usually not a problem. An alternative is to add oxidizing manganic
ions Mn4+ (MnO2 or pyrolusite) during manufacture which oxidize green Fe2+ to almost colourless Fe3+
(the black MnO2 is reduced to almost colourless Mn2+).
However for certain applications, e.g., optical fibres, the glass must be absolutely transparent
(100% transmittance or light or zero absorbance). Fibre optic cables transmit information as light pulses
rather than electic pulses. Optical fibres are usually double glass with an outer sheath of lower refractive
index which prevents light escaping out of the fibre. The high purity optical glass is drawn out into fine
fibres (5-100 µm diameter) which are then packed into bundles of several thousand. The bundles are
strong but retain the flexibility of individual fibres. Such a bundle of fibres can transmit 30 000 times
more information than an equivalent diameter copper communications cable as well as being cheaper and
lighter. Fibre optic technology has contributed to the communications revolution and a fibre optic cable
link Europe with the States and three cables link Japan with the States. An undersea fibre optic cable will
(or may already) connect the U.K. with Japan. Fibre optics are also used in endoscopes for internal
bodily examination and, in conjunction with lasers, in controversial key-hole surgery.
For other purposes many other different sorts of glass may be required. These are just a few other types of
glass:
 lead crytstal (or flint glass) - by the addition of lead
oxide gives a brilliant glass of high refractive index
that can be easily cut and polished is obtained,

 crown glass - 0% silicon 5% boron 57% phosphorus

used in lenses and other optical applications, barium
flint glass is used in bifocal lenses,
  amber glass - for protection of light sensitive liquids
(drugs, chemicals) contains Fe3+ and S2- which make
the glass dark brown, also green glass for wine (Fe2+
rich glass),

 cobalt blue glass - contains Co2+ and was formerly

used for poisons and by chemists in flame tests to
mask the yellow colour of sodium ion which is a
common contaminant,

 white opaque glass - is made by the addition of

calcium fluoride (CaF2 fluorspar) or stannic oxide
(SnO2) to the glass and is used in the food and drink
packaging industry,

 nuclear storage glass - molten glass is an excellent

solvent for metal oxides which are accommodated in
the voids in the structure; metallic nuclear waste
(caesium, cobalt, strontium etc.) is converted into
oxides and dissolved in molten glass (vitrification)
to give a relatively inert shiny black glass which is
stored in sealed steel containers underground in
geologically sound areas (nimby!),

 one-way glass, heat/light reflecting glasses,

low transmission, and insulating glasses are
designer glasses manufactured to meet a wide range
of security and construction purposes,

 optically variable or photochromic glass is used

in spectacles and car windows in sunny climates and
is borosilicate glass containing silver and copper
compounds - the silver ions are photochemically
reduced by copper ions to silver metal in strong
sunlight causing the glass to darken, when the light
fades the reverse reaction occurs and the glasses
becomes light again.
low light Cu+ + Ag+ -> Cu2+ + Ag strong light
Fibre glass is coarsely spun conventional glass and is widely used in insulation and the manufacture of
fireproof cloth (replacing dangerous asbestos) in safety curtains and fire blankets. Mixed with resins, glass
fibre forms light rigid materials for construction of boats, skis, canoes etc. Glass fibre filter papers are
used by chemists to filter corrosive solutions.
Also available - Introduction to Ceramics, written by Greg Geiger of The American Ceramic Society - Click
here
Please send comments, suggestions to:
Dr David Harrison(harrisond@newi.ac.uk)
or: Dr Clive Buckley(Buckleyc@newi.ac.uk)
Return To Science Help Page
Return To BA Primary Education Help Page
Updated: 31 October, 2000

http://www.newi.ac.uk/http://www.newi.ac.uk/

You are visitor since Feb 1997

Error! Filename not specified.