LECTURE 3

Advanced Polymers
PPE-308
Dr Atif Javaid

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[email protected]
Department of Polymer & Process
Engineering, UET, Lahore
Outline

 Carbon nanotubes (CNTs)

- Purification of CNTs
- Micro-fabrication of CNTs
- Chemical modification
- Wall Modification of CNTs
- Applications of CNTs
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).
How Multi-wall Carbon Nanotubes are fabricated?
Purification of Carbon nanotubes
• Presence of carbon nanoparticles and other impurities in
most of the assynthesized carbon nanotubes (typically,
30–70% w/w)
• Purification for retaining only the nanotubes becomes
essential
• Most commonly used purification method is the
oxidation of nanotube samples either in a gas or liquid
phase.
• Nanoparticles, more prone to oxidation, can be first burnt
away from the nanotubes in air above 700 °C and the
remaining pure (opened) nanotubes can then be separated
from each other by sonication in solvents (e.g. ethanol).
• Higher yields (up to 40% wt) have been achieved by
liquid-phase oxidation, for example, in KMnO4/ H2SO4
• Another non-destructive and size-selective purification
method is based on sonication and controlled flocculation
of nanotube samples in a surfactant solution followed by
filtration
 Closed
Micro-fabrication of Carbon nanotubes
• As-synthesized carbon nanotubes are closed at both ends.
Opening
• Tips of nanotubes are more reactive than their sidewalls, and hence
can be attached by various chemical reagents leading to the
opening of the nanotubes. Partially opened
• Carbon nanotubes can be either uncapped by oxidation with CO2
or O2 at high temperatures or opened through wet chemical
treatments with various oxidants (e.g. boiling in HNO3, H2SO4).
Filling
• Filling the hollow cores of CNTs with foreign materials is Opened
expected to have large impact on its potential applications.
• Filling can be accomplished either with preformed CNTs or during
the CNT formation. Both capillarity and surface wettability play
important roles in filling of preformed nanotube
• Liquids with low surface tensions (< 200 mN/m, common organic solvents), can wet
and fill CNTs, those with high surface tensions (> 200 mN/m, most pure metals) can not
wet CNTs. Filling with metals can be catalyzed with oxygen. Various metals including
Ni, Co, Fe, Ag, Au, Pd and Pt have been successfully filled into CNTs by filling them
with corresponding metal-containing inorganic precursor salts followed by chemical
reduction to the pure metal states (“nanowires”)
 Chemical Modification of Carbon nanotubes
• Difficult to synthesize carbon nanotubes with good surface characteristics as demanded for
various specific applications (e.g. strong interface with polymers in nanocomposites, good
biocompatibility for nanotube sensors).
• Therefore, surface modification and interfacial engineering are essential in making advanced
CNTs of good bulk and surface properties for various applications.
End-functionalization
• Solution chemical oxidation is found to be more efficient for the purification and/or
modification of carbon nanotubes.
• Oxidation reactions generate various functional groups (e.g. –COOH, –OH, –C=O) at the
opened end or defect sites of the carbon nanotube structure. Other groups may be also
introduced due to side reactions.
• Degree of oxidation depends strongly on oxidant nature and reaction conditions.
• –COOH and –OH groups of the oxidized nanotubes can be further used to covalently connect
other small and polymeric molecules through reactions characteristic of the end functionalities
 Outer Wall Modification of CNTs
Sidewall Fluorination of Carbon Nanotubes
• Chemical fluorination of CNTS has been achieved at relatively high temperatures
(250-400 ºC). As they are generally known to be inert towards fluorine at room
temperature.
• Above 400 C, fluorination damages the CNTS outer walls.
• Fluorination between 250 and 400˚C does not damage
the structure but reduces electrical conductivity due to
partial destruction of the graphitic structure.

Reaction Between Aniline and Carbon Nanotubes

• Carbon nanotubes show strong intermolecular
interaction leading to a solubility of SWNTs in
aniline up to 8 mg/ml. Chemical reaction may take
place between the SWNT and aniline.
• Grafted moieties can be removed by simply heating
the modified carbon nanotubes in an inert
atmosphere at 500 ˚C.
 Inner Wall Modification of CNTs
• Inner wall modification requires the opening of the nanotube tip(s) and the
protection of the outer wall of CNTs.
• Inner wall modification becomes easy if carbon nanotubes synthesized by the
template technique process.
1. Direct deposition of carbon nanotubes or their precursor polymer nanotubes
2. High-temperature graphitizing within the pores of a nanoporous template.
Oxidation of the inner surface of template-synthesized carbon nanotubes
• Nitric acid oxidation of nanotube inner walls within the nanoporous Al2O3 pores.
• Alumina template membrane act as the protection layer for the nanotube outerwall.
• After the completion of the inner wall oxidation, the template is removed by
dissolving it into an aq. HF to release the inner wall-modified nanotubes
Applications of CNTs
• Electrical
1. Field emission in vacuum electronics
2. Building block for next generation of VLSI
3. Nano lithography
• Energy storage
1. Lithium batteries
2. Hydrogen storage
3. Solar call
• Biological
1. Bio-sensors
2. Functional AFM tips
3. DNA sequencing
Applications

 Cement Based Foam Concrete Reinforced by Carbon Nanotubes

 Increases foam concrete’s compressive strength by up to 70%
making it comparable to conventional concrete at approximately
2800 psi
 50% less dense than conventional concrete with an average density
of under 70 lb/ft^3
 Easy to pour as a slurry
 Carbon nanotubes make up 0.05% of the mix by mass.
 Reduce heat conductivity between 12-20%
 Used in resins, which makes composite materials 20-30% stronger.
(Chemically bond to epoxy)
 Found in wind turbines, hunting arrows, and surfboards.
Energy Industry

• Carbon Nanotubes are being used in the energy

industry in Fuel Cells because of their high rate
of electron transfer.
• They are also being implemented as facilitators
of hydrogen storage on an experimental level.
Solar Cell

• Scientists have
developed the ‘blackest
black’ colour using
carbon nanotubes
• The carbon nanotubes
are arranged like blades
of grass in a lawn
- they absorb nearly all
light
• Use of carbon
nanotubes in solar cells
could vastly improve
their efficiency.
Sports goods
• Badminton racquet manufacturer
Yonex incorporates carbon
nanotubes into their cup stack
carbon nanotubes racquets
(www.yonex.com)
• American baseball bat manufacturer
Easton Sports has formed an
alliance with a nanotechnology
company Zyvex to develop baseball
bats incorporating carbon nanotubes
• Tennis racquets also incorporate
carbon nanotubes
(www.babolat.com).
AV Technology

• Carbon nanotubes are

being used to develop flat
screen televisions with
higher resolution than the
human eye can detect
• Your next TV screen
could be thin, ultra-light
and foldable…
Computer chips
• Most flash memory cells has 3 gates, about a micrometer
in between each.
• Using carbon nanotubes, the distance between these gates
can be shrunk by a factor of 1000, to the size of 1
nanometer.
• This means that much more memory can be held in the
same size chip.
Biomimics

Common Tern Ivory Gull

Squacco Stone Curlew

Biomimetic bat based on Carbon and

glass fibre composite at the University
of Stuttgart, Germany 2015
Advanced Aircrafts
Research and Development

• Hydrogen was successfully stored in nanotubes in

1997.
• Nanotubes and nanohorns are being used in
hydrogen storage and fuel cell research.
• Single crystals of SWCNTs are one solution to
storage issues
• Nanotube-polymer composite fiber research