LECTURE 2

Advanced Polymers
PPE-308
Dr Atif Javaid

OSO3H
OH
HO

HO3SO OSO3H
HO
OH
HO3SO OSO3H

OH
HO
OSO3H

atifjavaid@uet.edu.pk
Department of Polymer & Process
Engineering, UET, Lahore
Outline
 Nanotechnology
 Nano-Composites
- Introduction
- Types of Nano-composites
- Potential Benefits & Applications
 Carbon nanotubes (CNTs)
- Types of CNTs
- History of CNTs
- Properties of CNTs
- Non-covalent Chemistry of Carbon Nanotubes
- Fabrication of CNTs
What Makes Us Human?

Common Thing in all Ages!!!

Materials

Stone Age Bronze Age Iron Age Information Age ____???___ Age
“Hunter-Gatherer” “Agrarian” “Cities” “Computers” “Nanotechnology”
Learned to Learned to Learned to Learned to purify Learned to make
fashion tools smelt copper forge iron and silicon Czochralski nanoscale materials
from rock steel process
 Nanotechnology
• “Nano” comes from the Greek word “dwarf”.
• “A term referring to a wide range of technologies that measure,
manipulate, or incorporate materials and/or features with at least one
dimension between approximately 1 and 100 nanometers (nm). Such
applications exploit those properties, distinct from bulk or molecular
systems, of nanoscale components”. (ASTM E56)
• “Nanotechnology is science, engineering, and technology conducted at
the nanoscale, which is about 1 to 100 nanometers. Nanoscience and
nanotechnology are the study and application of extremely small things
and can be used across all the other science fields, such as chemistry,
biology, physics, materials science, and engineering”. (US Government
http://www.nano.gov/nanotech-101/what/definition)

Nanotechnology
Future
Wearable computers Smart Medicines Space Elevators
 What does 10nm mean?

Why go SMALL? GEOMETRY

More stuff, more surface

Smaller Things = More Devices

1 quartz crystal Thousand trillion grains of sand

Nanotechnology: A Paradigm Shift
• In Nanotechnology, what is important about materials is NOT really
what they are Made of, but how small they are. This is different
than every other materials age in human history.
• Richard Feynman – “Why can we not write the entire 24 volumes
of the Encyclopedia Brittanica on the head of a pin?”
http://calteches.library.caltech.edu/1976/

Nano
composites
Nano is now
Product “Nano Inside” Value Added

Active Ingredient:
Transparency
Nanoscopic TiO2/ZnO

Active Ingredient: Carbon

Strength and Bounce
Nanotubes

Embedded with “Nano Stain and Wrinkle

Whiskers” Resistance

http://www.nanotechproject.org/cpi/browse/nanomaterials/carbon-nanotube/
Search on carbon nanotubes: What is it with sports equipment!
Try fullerene – yes there are people who EAT nanomaterials
Nano Composites
• New class of particle filled polymer composites
• Nanocomposites are a broad range of materials consisting of two or more
components, with at least one component having dimensions in the nm
regime (i.e. between 1 and 100 nm)
• Typically consists of a macroscopic matrix or host with the addition of
nanometer-sized particulates or filler
• Three types of nanocomposites
1. Isodimensional nanoparticle based composites (all three dimensions
of nanoparticles are in nano-scale e.g. nano silica)
2. Nanotubes or whiskers based composites (two dimensions are in
nano scale and the third is larger, forming an elongated structure, e.g.
carbon nano tubes, cellulose whiskers or electrospun nanofibers
3. Polymer-layered crystal nanocomposites (one dimension in the
nanometer range, filler is present in the form of sheets of one to a
few nanometer thick to hundreds to thousands nanometers long
Polymer Layered Crystal Nano composites

Examples of layered
crystals subjected to
intercalation by a polymer

Chemical Nature Examples

Element Graphite
Metal chalcogenides (PbS)1.18(TiS2)2, MoS2
Metal phosphates Zr(HPO4)
Clays (layered silicates) Montmorillonite, hectorite, saponite,
fluoromica, fluorohectorite,
vermiculite, kaolinite, magadite
Layered double M6Al2(OH)16CO3·nH2O; M = Mg, Zn
hydroxides
Nano Composites

 Common matrix materials are rubber, engineering plastics

or polyolefines with a small content of nanoscale materials.
Usually less than 5% of nanomaterials are used to improve
thermal or mechanical properties

 Typical ways to produce Nanocomposites are In-Situ-

Polymerization and melt blending / compounding

 Three types of nano material are commonly melt blended

with plastics: Nano clay, nano tubes and nano scale
particles (SiO2, ZrO2, Ag)
 Nano Composites
 Resulting nanocomposite
may exhibit drastically
different (often enhanced)
properties than the
individual components
Lycurgus Cup
 Electrical, magnetic,
electrochemical,
catalytic, optical,
Lycurgus Cup is
structural, and made of glass.
mechanical properties Roman ~300 AD,
Myth of King
Lycurgus

Appears green in
reflected light and red
in transmitted light;
Most spectacular
glass of the period

http://www.britishmuseum.org/explore/highlights/highlight_objects/pe_mla/t/the_lycurgus_cup.aspx
Technology re-discovered in the 1600s and
used for colored stained glass windows
The Institute of Nanotechnology http://www.nano.org.uk/
 Why Nano Composites?
• Small filler size:
– High surface to volume ratio
• Small distance between fillers  bulk interfacial material
– Mechanical Properties
• Allow significant property improvements with very low loading levels
(Traditional microparticle additives require much higher loading levels to
achieve similar performance)
• Increased ductility with no decrease of strength,
• Scratching resistance
– Optical properties
• Light transmission characteristics particle size dependent

Microparticles Nanoparticles
 Nano Composites
Other Properties and Benefits

 Interaction of phases at interface is key:

 Adding nanotubes to a polymer can improve the strength (due to

superior mechanical properties of the NTs)

 A non-interacting interface serves only to create weak regions in

the composite resulting in no enhancement

 Most nano-particles do not scatter light significantly

 Possible to make composites with altered electrical or mechanical

properties while retaining optical clarity

 CNTs and other nano-particles are often essentially defect free

 Nano Composites
Potential Benefits & Applications
Nanoclays in Polymers
 Liquid and Gaseous barriers
 Food packaging applications (processed meats, cheese, cereals) to
enhance shelf life
 Reduce solvent transmission through polymers such as
polyamides for fuel tank and fuel line components
 Reduce water absorption in polymers (environmental protection)
 Reduction of flammability of polymeric materials (e.g. polypropylene)
with as little as 2% nanoclay loading
 Definition:
Carbon Nanotube and Carbon fiber

• The history of carbon fiber goes way

back…
• The history of carbon nanotube starts
from 1991
• Carbon nanotubes, composed of
interlocking carbon atoms, are 1000x
thinner than an average human hair –
but can be 200x stronger than steel.
• The first synthetic material to have
greater strength than spider silk
• Excellent conductors of electricity
and heat
Carbon nanotube

CNT: Rolling-up a graphene sheet to form a tube

Schematic STM image

of a CNT of CNT
Covalent bonding in Carbon nanotube
• Carbon nanotubes are formed by a
layer of hexagonally-arranged
carbon atoms rolled into a
cylinder
• Electrons are localised internally,
and some can move along the
length of the tube by ballistic
transport
• Carbon nanotube diameter ~ 1nm
• Carbon nanotube length can be a
million times greater than its
width
Different types of Nanotubes
There are two types of carbon nanotubes: Multi
walled nanotubes (MWNT) and Single walled
(SWNT). Multi walled have multiple layers of
carbon nanotubes around a single one, whereas
single walled have only one layer.
- single-walled (d = 1-2 nm), or
- multi-walled (d = 5-80 nm).
Size of Carbon nanotube
History
• The discovery of multi-wall
carbon nanotubes was in 1991.
• The single-wall nanotubes
were discovered in 1993
• Synthesis of nanotube
peapods in 1998

• Hydrogen storage in nanotubes

in 1997
 History

Endo synthesizes
Bacon produces CVD (Chemical Kroto, Smalley,
carbon fibers Vapor Deposition) Iijima synthesizes
and Curl
with arc growth of nanometer- discover
multiwall carbon
discharge scale carbon fibers fullerenes nanotubes

1958 1976 1985 1991

 History

Iijima and Bethune

Harris, Tsang, Rice University Iijima produces
simultaneously
et al. produce directly produces and names
discover singlewall
nanohorns nanotube bundles nanohorns
nanotubes

1993 1994 1996 1998

 History
Nanotubes were
Nature published a alloyed into the
photo of an Nanotube sheet Researchers
carbon fiber bike
individual 4 cm synthesised with build a Carbon
that won the
long single-wall dimensions 5 × nanotube
2006 Tour de
nanotube (SWNT) 100 cm computer
France

2004 2005 2006 2015

Properties
• Carbon-carbon bonds
are one of the strongest
bond in nature
• Carbon nanotube is
composed of perfect
arrangement of these
bonds
• Extremely high Young’s
modulus

Material Modulus
(GPa)
Steel 190-210
SWNT 1,000+
Diamond 1,050-1,200
CNTs in CFRP Composites
 How Nanotubes are fabricated?
Rice University group (1996)-- produce bundles of ordered single-wall
nanotubes :
1. Prepared by the laser vaporization of a carbon target in a furnace at
1200 °C.
2. Cobalt-nickel catalyst helps the growth of the nanotubes,
presumably because it prevents the ends from being "capped"
during synthesis.
3. By using two laser pulses 50 ns apart, growth conditions can be
maintained over a larger volume and for a longer time. This scheme
provides more uniform vaporization and better control of the
growth conditions.
4. Flowing argon gas sweeps the nanotubes from the furnace to a
water-cooled copper collector just outside of the furnace.
http://nanohub.org/resources/96/about
How Multi-wall Carbon Nanotubes are fabricated?
Operating a carbon arc discharge generator with a DC current
of 50–100 A and voltage of 20–25 V at a discharge
temperature above 3000˚C under an inert atmosphere (e.g. He).