Cement & concrete

Constituent
Tricalcium
Silicate
Dicalcium
Silicate
Tricalcium
Aluminate
Tetracalcium
aluminofeeri
te
Others

Symbol
C3S

%
45

C2S

30

C3A

10

C4AF

Cement contd.
Portland cement consists of a number of
silicate minerals
Cement mixed with water sets as a function
of time due to several hydration reactions
Water binds the sheet like silicate
molecules together, thereby hardening the
cement
Concrete sized aggregate of rocks
embedded in a cement matrix, which binds
the rock pieces together

Polymers

Many simple molecules (monomer) unite to

give a big molecule, called polymer
Organic polymers thousands of monomers
are united by covalent bonds formed by carbon
Because electrons are strongly bonded, they
are localized and polymers are thermal and
electrical insulators
Relatively inert do not corrode due to
covalent bonding

Polymers

Classification:
(i) thermoplasts (ii) thermosets
Thermoplasts:
Long chain polymerization, proceeds linearly
have increasing plasticity, i.e., increasing ability to
deform plastically with increasing temperature
Long chain molecules are held together by secondary
bonds
Secondary bonds between the chains are broken more
readily therefore easily mouldable and finally melts

Polymers contd.
Thermosets:
Three dimensional net work of primary bonds
because polymerization proceeds in all directions
Relatively hard at room temperature and do not
soften on heating
Become harder due to completion of any let-over
polymerization reaction
Decompose before melting due to their reaction
with atmospheric oxygen
Ex: Bakelite used for electrical insulation

Long chain polymers

Classification
(i) Plastics (ii) fibers (iii) elastomers
Plastics:
No directional property long chain molecules are
randomly oriented
Fibers:
All chains are more or less aligned in the long
direction of the fiber - unique directional property

Contd.
Elastomers:
Long chain molecules exhibiting the
unique rubbery behaviour
Structure of long chain polymers:
H

-C=CH

-C-CH

Contd.
sp3 hybridization tetrahedrally bonded
R1
R3
R2
R4
monomer

Contd.
Degree of polymerization
This is the No. of repeating monomers in a

chain
M.wt of polymer = degree of polymerization x
m.w of
monomer
M.w in the range 10 000 to 1 000 000

Name

Monomer unit
Uses
R1 R2 R3 R4

Polyethylene
(polythene)

Polyvinyl chloride H
(PVC)

Cl Electrical
insulation,
gramaphone
records

H H

Polypropylene

Sheets,tubes,
Containers

CH3 Ropes,filaments,
vacuum
flasks,flashlight
casings

Polymethylmetha H H CH3
crylate(Plexiglass COOCH3
)

Transparent
windows &
fixtures

Polystyrene

Styrofoam, sound

H H

H C6H5

Polytetrafluoroeth F F
ylene(PTFE)
(Teflon)

Poyacrylonitrile
(Orlon)

H H H CN

Coating for frying

pans, razors and
bearings,
chemical
ware,human
body implants

Acrylic fiber used

as wool
substitute in
clothings

Polyamide fibers
O

-C N - linkageEx: nylon (6,6) NH(CH2)6NHCO(CH2)4COH

Hydrogen bonding between
adjacent chains
monomer
Hydrogen bonds stronger than van der Waals
bonds greatest resistance of nylons to softening
with increase in temperature

CH2
CH2

N
C

CH2
CH2

CH2

CH2

CH2
CH2

C
N

CH2
N
CH2
CH2
CH2
C
CH2
CH2
CH2
CH2
N
CH2

Polyester fibers
O

- O C linkage terylene or dacron

O is present in the backbone chain
instead of C provides flexibility
polyester softens easily with
increasing temperature in spite of
the hydrogen bonding between
chains

cellulose
Main

constituent of wood is the

cellulose chain the monomer
formula is:

CH2OH

CH O
- O CH
CH

CH CH

HO
OH

Contd.
Alignment of long chains gives wood its highly
directional properties
Tensile strength more in the longitudinal
direction compared to transverse direction
Rayon-i.e., regenerated cellulose is natural
cellulose rendered highly crystalline
Cotton is related to natural plant fiber
If the wrinkles in the long chain molecules of
cotton are removed permanently, shrink
resistant, sanforized cotton is obtained

Natural rubber
Isoprene is the monomer unit
Side groups in the monomer are both on
the same side of the molecule this is the
reason for the natural tendency for the
molecule to bend and promote rubbery
behavior
H

H CH3

C=CC=C
H

H H CH3H
CC=CC-H
H

Contd.
Natural rubber tapped from tree is a viscous
liquid long isoprene molecules are able to flow
past one another at room temperatures
Raw rubber heated with S gives elastomer
cross linking takes place the process is called
vulcanization, remaining double bond also gets
saturated
Degree of vulcanization determines the stiffness
of rubber
Cross links increased rubber becomes more
rigid

Contd.
Ex: cycle tube is less vulcanized than a
rubber tyre
When all the double bonds are used up by
sulfur bridges, a three dimensional
network of primary bonds results
Ex: ebonite hard and brittle

Crystallinity of long chain polymers

Long

chain polymers usually noncrystalline or in the semicrystalline

form
Non-crystalline form long chains
are randomly twisted with one
another

Crystallinity of long chain polymers

Semicrystalline parts of the polymer
volume have the parallel chain
arrangement, while other parts are
randomly oriented
Sometimes single crystals of polymers can
be grown crystals have a folded chain
structure, where the same chain folds back
and forth many times into a parallel
arrangement
Single crystal of polythene has an
orthorhombic unit cell

Making a crystal of polymer

In all polymers, long chains can be aligned
to some extent by mechanical working
such an alignment promotes crystallinity
High density polyethylene(sp.gr. 0.97)
In crystalline form, chains are more
closely packed density increases with
increasing alignment of the chains, 80%
crystalline)
Low density polyethylene (sp.gr. 0.92)
Less than 50% crystalline compared to
high density polyethylene

Cryatallinity (contd.)
Crystallinity

is also promoted by the

formation of a hydrogen bond
between chains instead of weaker
van der Waals bond.
Ex: nylon and cellulose crystallize
due to the hydrogen bond.

Factors promoting non-crystallinity

Very long chains get tangled (coiled) easily

more difficult to crystallize

Branching impedes crystallization prevents
the parallel arrangement of chains necessary
for crystallization
Irradiation of polymers can knock off a small
side group such as hydrogen, where the end
of another molecule can be bonded,
producing a branched structure branching
makes the polymer stiffer

Different arrangements of
polymers
Atactic:

large side groups are randomly

arranged on either side of the chain
crystallization is difficult because the
arrangement does not allow neighboring chains
to come closer all along the length of the chain
Isotactic: all the bulky groups are arranged on
the same side
Syndiotactic: bulky side groups alternate on
either side of the chain in a regular fashion
Isotactic and syndiotactic promote crystallinity
Copolymer: two or more monomers are
polymerized together-promote noncrystallinity