Polymers: Classification

A) Thermoplastics such as polyethylene, which

soften on heating.
B) Thermosets or resins such as epoxi which
harden when two components are heated
together.
C) Elastomers or rubbers
D) Natural polymers such as cellulose, lignin
and protein, which provide the mechanical basis
of most plant and animal life

From: Asby& Jones

CE 60
Instructor: Paulo Monteiro

Engineering Thermoplastics
This term was first introduced by the General Electric
Co. in the 1960s, & they defined it as a polymer alloy
which could replace metals in many applications.
Polyethylene is the most common of them. It is a linear
polymer. That is why they soften when heated.
Thermoplastics are made by adding together
(polymerizing) sub-units (monomers) to form long
chains.
H H
Example:

-C - C
H R

R may be hydrogen (polyethylene), or

CH3 (polypropylene) or Cl (polyvinylchloride)

CE 60
Instructor: Paulo Monteiro

A high-molecular-weight polyethylene has an average molecular weight

of 410,000 g/mol. What is its average degree of polymerization?
mass of the polyethylene mer :
(4 hydrogen atoms 1 g/mol) + (2 carbon atoms 12 g/mol) = 28
g/mol.

molecular weight of polymer (g / mol)

DP =
molecular weight of mer (g / mol / mer)
410, 000 g / mol
=
28 g / mol / mer
= 14, 643 mers

Thermoplastics

Nylons are one example of an engineering

thermoplastic.
Polycarbonates have a ring structure in
the chain which makes it very stiff
molecule which translates into a high
melting point.

CE 60
Instructor: Paulo Monteiro

What type of bonding exists within

the molecular chains of
thermoplastics?
Within thermoplastic molecular chains,
covalent bonds exist.

Thermosetting Plastics

Thermoplastics are usually easier to mold into complex shapes. The

polymer is heavily cross-linked
but thermosetting polymers offer more of the following properties:
High thermal stability
High rigidity
High dimensional stability
Resistance to creep & deformation under load
Light weight (as compared to metals)
High electrical & thermal insulating properties
Today many thermosetting resins are available which have
superior properties. [See p. 330-340 in the Smith textbook].

CE 60
Instructor: Paulo Monteiro

Describe the atomic structural

arrangement of thermosetting
plastics.
Most thermosetting plastics consist of
three-dimensional networks of covalently
bonded atoms, as compared to the long
chain-like molecules of thermoplastics.

Elastomeric Materials
Elastomers are linear polymers with
occasional-cross links. These cross-links
provide a memory so it returns to its
original shape on unloading.
Polymers which show rubbery behavior
at their operating temperature are called
elastomeric [See the Smith textbook].
Some elastomeric polymers are
thermoplastics & others are thermosetting.
The prototype is natural rubber.
CE 60
Instructor: Paulo Monteiro

Glassy plateau

E
Glass transition
Rubbery plateau
Viscous flow

Temperature
CE 60
Instructor: Paulo Monteiro

Portland Cement

A hydraulic cement capable of setting, hardening and

remaining stable under water. It consists essentially of
hydraulic calcium silicates, usually containing calcium
sulfate.

CE 60
Instructor: Paulo Monteiro

Manufacture

Raw Materials:
2/3 calcareous materials (lime bearing) - limestone
1/3 argillaceous materials (silica, alumina, iron)- clay

CE 60
Instructor: Paulo Monteiro

Based on the following notation:

C

CaO

SiO2

Al2O3

Fe2O3

H2O

CE 60
Instructor: Paulo Monteiro

Cement Minerals

C3S : 3CaOSiO2
C2S : 2CaOSiO2
C3A : 3CaOAl2O3
C4AF : 4CaOAl2O3Fe3O4

CE 60
Instructor: Paulo Monteiro

CHEMICAL REACTIONS

2C3S + 6H --> C3S2H3 + 3CH + 120 cal / g

2C2S + 4H --> C3S2H3 + CH + 62 cal / g
C3A + CSH2 --> Ettringite + 300 cal / g

CE 60
Instructor: Paulo Monteiro

SOLIDS IN CEMENT PASTE

-Calcium Silicate Hydrate
Notation: C-S-H
C/S Ratio: 1.5 to 2.0
Main Characteristics: High Surface (100 to 700 m2/ g) ----> High Van
der Walls Force -----> Strength.
Volume % : 50 a 60

CE 60
Instructor: Paulo Monteiro

SOLIDS IN CEMENT PASTE

-Calcium Hydroxide ( portlandite)
Ca(OH)2
Volume % : 20 to 25
low Van der Walls force
problems with durability and strength
CE 60
Instructor: Paulo Monteiro

SOLIDS IN CEMENT PASTE

-Calcium Sulfoaluminate Hydrates
Volume % : 15 to 20
first : ettringite
after : monosulfate hydrated.

CE 60
Instructor: Paulo Monteiro

Hydration process Initial Condition

Lets study a cement paste with w/c= 0.63

Start with 100 cm3 of cement.
Compute the mass of cement: Mc = 3.14* 100 = 314 g
Compute the mass of water: Mw = 0.63 * 314 = 200 g
Vw= 200 cm3

Vc= 100 cm3

CE 60
Instructor: Paulo Monteiro

ASTM Portland Cements

Type I-

General Purpose

Type II- moderate heat of hydration and sulfate resistance (C3A <
8%) : general construction, sea water, mass concrete
Type III- high early strength (C3A < 15%) : emergency repairs,
precast, winter construction.
Type IV- low heat ( C3S < 35%, C3A < 7%, C2S > 40%) : mass
concrete
Type V-

sulfate resistant ( C3A < 5%) : sulfate in soil, sewers.

CE 60
Instructor: Paulo Monteiro

Aggregates
cost
provide dimensional stability
influence hardness, abrasion resistance,
elastic modulus

CE 60
Instructor: Paulo Monteiro

Aggregate Type

Coarse aggregate ( > 3/16 in. - 4.75 mm of No. 4)

Fine aggregate < 3/16 in. and > 150 (No. 200)

CE 60
Instructor: Paulo Monteiro

Aggregate Type -mineralogy

Sedimentary Rocks (cost effective - near the surface),
about 80% of aggregates
Natural sand and gravel
Sandstone, limestone (dolomite), chert, flint, graywacke
Metamorphic Rocks: slate, gneiss : excellent
to poor

CE 60
Instructor: Paulo Monteiro

CE 60
Instructor: Paulo Monteiro

 Fineness modulus is the sum of the total

percentages retained on each of the
specified sieve divided by 100. The
specified sieves are 3, 1 1/2, 3/4 and 3/8
in and Nos. 4, 8, 16, 30, 50 and 100.

CE 60
Instructor: Paulo Monteiro

Characteristics of coarse aggregate

Characteristics of fine aggregate
Type Used:________________
Type Used: ______________
Max. Size:______1______ inch
F.M. _____2.93______________
B.S.G: 168 ______lb/ft3
B.S.G: 167 ______lb/ft3
Moisture deviation from S.S. D.=_-0.4%__ Moisture deviation from S.S. D.=0.7%__
Dry-rodded unit wt.__104_lb/ft3____
B.S.G of cement = 196 lb/ft3

CE 60
Instructor: Paulo Monteiro

Effect of moisture

CE 60
Instructor: Paulo Monteiro

Types of Elastic Modulus

Testing

ASTM Testing

CE 60
Instructor: Paulo Monteiro

Creep and Shrinkage

CE 60
Instructor: Paulo Monteiro

Importance

CE 60
Instructor: Paulo Monteiro

Compressive Strength
Fundamental relationship
S = So exp (-kp)
Where So is the strength at zero
porosity, p is the porosity and k a
constant.
CE 60
Instructor: Paulo Monteiro

Interfacial Transition Zone

CE 60
Instructor: Paulo Monteiro

REASON

CE 60
Instructor: Paulo Monteiro

Microstructural improvement
Use of silica fume
reduce the porosity of the ITZ
geometrical effect (no space)
reduces the amount of CH due to
pozzolanic reaction
CE 60
Instructor: Paulo Monteiro

Humidity
Great importance of moist curing.

CE 60
Instructor: Paulo Monteiro

Temperature
Cast and cured at the same temperature
Cast at different temperature but cured at
the same temperature
Cast at normal temperature but cured at
different temperatures.
CE 60
Instructor: Paulo Monteiro

Testing parameters
Specimen Size: Fracture mechanics will
explain the importance of size effect.
Loading Rate: Increasing rates lead to
increasing strength.
CE 60
Instructor: Paulo Monteiro

CE 60
Instructor: Paulo Monteiro

Thermal stresses

t = K r

E
1+

where:
t: tensile stress
Kr: degree of restraint
E: elastic modulus
: coefficient of thermal expansion
T: temperature change
: creep coefficient
CE 60
Instructor: Paulo Monteiro

Temperature Evolution

T = placement temperature of fresh concrete + adiabatic temperature rise

- ambient or service temperature - heat losses.
CE 60
Instructor: Paulo Monteiro

Durability

Durability of concrete: ability to resist

weathering action, chemical attack,
abrasion, or any process of
deterioration

CE 60
Instructor: Paulo Monteiro

Water Structure

CE 60
Instructor: Paulo Monteiro

Abrasion - Erosion

Note: the deterioration starts at the surface,

therefore special attentions should be given
to quality of the concrete surface.
Avoid laitance (layer of fines from cement and
aggregate).

CE 60
Instructor: Paulo Monteiro

The problem

The transformation of ice from liquid water generates a volumetric

dilation of 9%. If the transformation occurs in small capillary pores,
the ice crystals can damage the cement paste by pushing the capillary
walls and by generating hydraulicCEpressure.
60
Instructor: Paulo Monteiro

Deterioration by fire

Concrete is able to retain sufficient strength

for a reasonably long time.

CE 60
Instructor: Paulo Monteiro

Effect of High Temperature on

Cement Paste
(a) degree of hydration
(b) moisture state
de-hydration:
ettringite > 1000C
Ca(OH)2 500-6000C
CSH ~ 9000C
CE 60
Instructor: Paulo Monteiro

Electrochemical process of steel corrosion in concrete

CE 60
Instructor: Paulo Monteiro

Volumetric change

CE 60
Instructor: Paulo Monteiro

The chemistry is simple

1) The high pH in the cement paste promotes the hydrolysis of silica
Si-O-Si + H OH Si-OH+ Si-OH
aggregate paste
2) Si-OH react with the paste to form Si-O3) Si-O-, adsorbs Na, K, and Ca to form a gel.

CE 60
Instructor: Paulo Monteiro

Expansive Reaction
In the presence of sulfates

C3A + gypsum C3A.3C$.H32 (ettringite)

C3A.C$.H18 (monosulfate)

CE 60
Instructor: Paulo Monteiro

Sodium sulfate attack:

Na2SO4 +Ca(OH) 2 +2H2O
CaSO4.2H2O + 2NaOH
the formation of sodium hydroxide as a by-product
of the reaction ensures the continuation of high
alkalinity in the system, which is essential for the
stability of the cementitious material C-S-H.
CE 60
Instructor: Paulo Monteiro

Magnesium sulfate attack

MgSO4 +Ca(OH) 2 +2H2O

CaSO4.2H2O + Mg(OH) 2
3 MgSO4 + 3CaO .2SiO2 .3H2O + 8 H2O 3 CaSO4.2H2O + 3
Mg(OH) 2 + 2SiO2.H2O

the conversion of calcium hydroxide to gypsum is accompanied

by the simultaneous formation of relatively insoluble magnesium
hydroxide.
In the absence of hydroxyl ions in the solution C-S-H is no
longer stable and is also attacked by the sulfate solution.
The magnesium sulfate attack is, therefore, more severe on
concrete.
CE 60
Instructor: Paulo Monteiro

Factors influencing sulfate attack

amount and nature of the sulfate present,

level of the water table and its seasonal
variation,
flow of groundwater and soil porosity,
form of construction,
quality of concrete.
CE 60
Instructor: Paulo Monteiro

Determine the lattice points per cell

in the cubic system

Simple cubic:
Lattice points are located only at the corners of the cube
8 corners (1/8) = 1
In BCC unit cells, lattice points are located at the corners and the center of the cube:
8 corner (1/8) + 1 center (1) = 2
In FCC unit cells, lattice points are located at the corners and faces of the cube:
8 corners (1/8) + 6 faces (1/2) = 4

CE 60
Instructor: Paulo Monteiro

Calculate the radius of an atom that

will just fit into a cubic site

2R + 2r= 2R sqrt(3)
r/R = 0.732

R
2R + 2r= 2R sqrt(3)

2R

CE 60
Instructor: Paulo Monteiro

Problem
Calculate the change in volume that
occurs when BCC iron is heated and
changes to FCC iron. The lattice
parameter of BCC iron is 2.863 A and of
FCC iron is 3.591 A
Volume of BCC cell = a3 = 2.863 = 23.467
Volume of FCC cell = a3 = 3.591 = 46.307
But the FCC unit cell contains four atoms and the BCC unit cell contains only two
atoms. Two BCC unit cells with a total volume of 46.934 will contain 4 atoms.
Volume change/atom = (46.307 -46.934)/46.934 = -1.34%
Steel contracts on heating!!
CE 60
Instructor: Paulo Monteiro

Hypoeutectoid Phase Diagram

If a steel with a composition x% carbon is cooled from the Austenite
region at about 770 C ferrite begins to form. This is called
proeutectoid
(or pre-eutectoid) ferrite since it forms before the
pro
eutectoid temperature.

CE 60
Instructor: Paulo Monteiro

Problem

CE 60
Instructor: Paulo Monteiro

An Example
(Assume a Eutectoid Low Carbon Steel)

(a) Water-quench to room Temperature.

(b) Hot-quench at 690C & hold 2 hr; water-quench
(c) Hot-quench at 610C
& hold 3 min; water-quench

Pearlite
Pearlite

(d) Hot-quench at 580C

& hold 2 sec; water-quench
Bainite

(e) Hot-quench at 450C &

hold 1 hr; water-quench

50% pearlite + 50 martensite

CE 60
All martensite
Instructor: Paulo Monteiro

Types of Atomic & Molecular Bonds

Primary Atomic Bonds

Ionic Bonds
Covalent Bonds
Metallic Bonds

Secondary Atomic & Molecular Bonds

Permanent Dipole Bonds
Fluctuating Dipole Bonds

CE 60
Instructor: Paulo Monteiro