3. INTRODUCTION
• Carbon nanotubes (CNTs) are hexagonally shaped arrangements of
carbon atoms that have been rolled into tubes.
• Diameter: less than 1 nm.
• Length: from a few nanometers up to a millimeter.
• Rolling up a graphene sheet may lead to a CNT (For imagination only!).
Adopted from “http://www.physik.uni-regensburg.de”
what are they?
INTRODUCTION: HistoryINTRODUCTION
What are they?
3
4. INTRODUCTION: History
• 1952:
Radushkevich and Lukyanovich showed hollow graphitic carbon fibers
with 50nm diameter.
• 1979
Abrahamson presented evidence of carbon nanotubes at the 14th Biennial
Conference of Carbon at Pennsylvania State University.
• 1981
A group of Soviet scientists published the results of chemical and structural
characterization of carbon nanoparticles produced by a thermocatalytical
disproportionation of carbon monoxide.
• 1991
Nanotubes discovered in the soot of arc discharge at NEC, by Japanese
researcher Sumio Iijima.
INTRODUCTION
History
4
6. INTRODUCTION: CNT types
Multiple Wall CNT
or
Single Wall CNT
or
Parchment model Russian doll model
INTRODUCTION: HistoryCNT types
Based on walls
6
7. PROPERTIES: Mechanical
• Carbon nanotubes are the strongest, flexible and stiffest materials yet
discovered in terms of tensile strength and elastic modulus respectively.
• The hardness (152 Gpa) and bulk modulus (462–546 Gpa) of carbon
nanotubes are greater than diamond, which is considered the hardest material.
• The current Young’s modulus value of SWCNs is about 1 terapascal.
• The modulus of the multi walled carbon nanotubes correlates to the amount
of disorder in the carbon nanotube walls.
• when multi walled carbon nanotubes break, the outermost layers break first
Materials Young’modulus(Tpa) Tensile strength(Gpa) Elongation at
break(%)
SWNTE ~1 (from 1 to 5) 13-53 16
Armchair
SWNTT
0.94 126.2 23.1
Zigzag SWNTT 0.94 94.5 15.6-17.5
Chiral SWNT 0.92
MWNTE 0.2-0.8-0.95 11-63-150
Stainless steelE 0.186-0.214 0.38-1.55 15-50
KevlarE 0.06-0.18 3.6-3.8 ~2
EExperimental observation; TTheoretical prediction
INTRODUCTION: HistoryPROPERTIES
Mechanical
7
8. PROPERTIES: Electrical conductivity
• CNTs can be metallic or semi-conductors due to their geometry.
• For a given (m,n) nanotube:
- If n=m (armchair) the CNTS is metallic
- If n-m is multiple of 3 the CNTs is semiconducting with a
small band gap.
- Otherwise ,the CNTs is moderate semiconductor.
• In theory, metallic nanotubes can carry an electric current density of
4 × 109 A/cm2, which is more than 1,000 times greater than those of
metals such as copper.
• They are one dimensional conductors only along the axis
INTRODUCTION: HistoryPROPERTIES
Electrical conductivity
8
9. PROPERTIES: Thermal conductivity
• SWNTs room-temperature thermal conductivity is about 3500 W/(m·K) and
over 3000 W/(m·K) for individual MWNT.
• Addition of nanotubes to epoxy resin can double the thermal conductivity for a
loading of only 1%, showing that nanotube composite materials may be useful
for thermal management applications.
• All nanotubes are expected to be very good thermal conductors along the tube,
but good insulators laterally to the tube axis.
INTRODUCTION: HistoryPROPERTIES
Thermal Conductivity
9
10. PROPERTIES: Thermal conductivity
• Flourescence:
Semiconducting SWCNTs emit and absorb NIR.
No excitonic luminescence in metallic tubes.
Photoluminescence is used for measuring the quantities of semiconducting
nanotube species in a sample.
Also to identify the symmetry and (n,m) properties.
• Raman spectroscopy:
Raman spectroscopy has provided an exceedingly powerful tool for
characterization of CNT’s with respect to their diameters, and quality of the
samples properties.
SWCNT and MWCNT can be discriminated via this method.
INTRODUCTION: HistoryPROPERTIES
Optical
10
11. SYNTHESIS
• The most common and perhaps easiest way to produce CNTs.
• Carbon contained in the negative electrode sublimates because of the
high-discharge temperatures.
• The yield for this method is up to 30% by weight and it produces both
single- and multi-walled nanotubes with lengths of up to 50 micrometers
with few structural defects.
• Produces a complex mixture of components, and requires further
purification - to separate the CNTs from the soot and the residual catalytic
metals present in the crude product.
INTRODUCTION: HistorySYNTHESIS
I. Arc discharge method
11
12. SYNTHESIS
• A substrate is prepared with a layer of metal catalyst particles, most commonly
nickel, cobalt, iron , or a combination.
• The substrate is heated to approximately 700°C.
• two gases are bled into the reactor: a process gas (such as ammonia , nitrogen or
hydrogen ) and a carbon-containing gas (such as acetylene , ethylene , ethanol or
methane ).
• Nanotubes grow at the sites of the metal catalyst; the carbon-containing gas is broken
apart at the surface of the catalyst particle, and the carbon is transported to the edges
of the particle, where it forms the nanotubes.
• Attracted attentions for its feasibility and potential for large-area production with
reasonable growth rates at relatively low temperatures.
INTRODUCTION: HistorySYTHESIS
II. Chemical vapor deposition (CVD)
12
13. SYNTHESIS
• A pulsed laser vaporizes a graphite target in a high-temperature reactor while an
inert gas is bled into the chamber.
• Nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon
condenses.
• A water-cooled surface may be included in the system to collect the nanotubes.
• The laser ablation method yields around 70% and produces primarily single-
walled carbon nanotubes with a controllable diameter determined by the reaction
temperature .
• However, it is more expensive than either arc discharge or chemical vapor
deposition.
INTRODUCTION: HistorySYNTHESIS
III. Laser ablation
13
14. APPLICATIONS
• More slender tips higher resolution will gain in microcopy.
• In addition, due to the high elasticity of the nanotubes, the tips do not suffer from
crashes on contact with the substrates.
• Biological molecules, such as DNA can also be imaged with higher resolution using
nanotube tips, compared to conventional STM tips.
INTRODUCTION: HistoryAPPLICATION
I. AFM/STM Tips
14
Tang et al., Nano Lett. 5(1), 11-14 (2005).
Si Tip
CNT Probe
Chang et al., Jpn. J. Appl. Sci. 43(7B), 4517-4520 (2004).
Chang et al., Jpn. J. Appl. Phys. 43(7B), 4517-4520 (2004).
16. APPLICATIONS
• An important issue in intracellular drug delivery is the poor permeability of
the plasma membrane to many drugs.
• Thus, various carriers, including polyethylene glycol, peptides and lipids,
have been developed to facilitate the cellular entry of drugs.
• Recently, the feasibility of using SWNTs for intracellular drug delivery has
been demonstrated.
• They have high drug loading capacities and good cell penetration
qualities.
• Problems: lack of solubility, clumping occurrences, and half-life
INTRODUCTION: HistoryAPPLICATION
III. Molecular carriers
16
17. APPLICATIONS
• Semi-conductive SWNTs with appropriate chirality can generate a small
band gap fluorescence of 1 eV, which corresponds to NIR range (900-1600
nm).
• Biological tissues have very low absorption, scattering, and
autofluorescence in this range and therefore, are very useful for biological
imaging.
• CNTs show great promise in NIR photoluminescence imaging , Raman
imaging and optical absorption agent for photoacoustic imaging.
INTRODUCTION: HistoryAPPLICATION
IV. Biomedical imaging
17
18. APPLICATIONS
• A biosensor is a bioanalytical
device consisting of 2
components:
a bioreceptor and a transducer.
• The bioreceptor is a
biomolecule that recognizes the
target analyte whereas the
transducer converts the
recognition event into a
measurable signal.
INTRODUCTION: HistoryAPPLICATION
V. Bio-sensing
18
19. • SWNT biosensors can exhibit large changes in electrical impedance and
optical properties in response to the surrounding environment which is
typically modulated by adsorption of a target on the CNT surface.
• Low detection limits and high selectivity require engineering the CNT surface
(e.g., functional groups and coatings).
• CNT plays dual role in a biosensor both as immobilization matrices and as
electron mediator.
V. Bio-sensing
19
20. CHALLENGES
• Cost: Too expensive (~ $ 200per gram)
• Toxicity: there are some reports showing CNTs can
damage DNA or causing pulmonery toxicity.
• Manipulation: hard to purify and the ability to
manipulate structures at the atomic scale.
• Large-scale production: Large quantity fabrication
process still missing.
20
21. SUMMARY
• CNTs have special properties which makes them interesting
in many fields.
• There is still a great need of improving its production and
manipulation.
• In biotechnological applications, we must care especially
when studying them for biomedical applications.
• Using CNTs for us biotechnologists needs a team work
since a deep knowledge will be gained when working in
interdisciplinary discipline!
21
22. • Shao, Wei, et al. "Carbon Nanotubes for Use in Medicine: Potentials and
Limitations." (2013).
• Ajayan, Pulickel M., and Otto Z. Zhou. "Applications of carbon
nanotubes."Carbon nanotubes. Springer Berlin Heidelberg, 2001. 391-425.
• Balasubramanian, Kannan, and Marko Burghard. "Biosensors based on
carbon nanotubes." Analytical and bioanalytical chemistry 385.3 (2006):
452-468.
• Popov, Valentin N. "Carbon nanotubes: properties and
application." Materials Science and Engineering: R: Reports 43.3 (2004):
61-102.
22
KEY REFERENCES
In the Russian Doll model, sheets of graphite are arranged in concentric cylinders, e.g., a (0,8) single-walled nanotube (SWNT) within a larger (0,17) single-walled nanotube.
In the Parchment model, a single sheet of graphite is rolled in around itself, resembling a scroll of parchment or a rolled newspaper.
The interlayer distance in multi-walled nanotubes is close to the distance between graphene layers in graphite, approximately 3.4 Å. The Russian Doll structure is observed more commonly. Its individual shells can be described as SWNTs, which can be metallic or semiconducting.
Elastic Like Plastic
Light Like Aluminum
Strong Like Steel
kevlar: paraaramid alyaf
55 tensile
Because of the symmetry and unique electronic structure of graphene, nanotube has a very high current carrying capacity.
Single –walled CNTs exhibit electric properties that are not shared by the multi-walled CNTs variant
However, this rule has exceptions, because curvature effects in small diameter carbon nanotubes can strongly influence electrical properties. Thus, a (5,0) SWCNT that should be semiconducting in fact is metallic according to the calculations. Likewise, vice versa—zigzag and chiral SWCNTs with small diameters that should be metallic have finite gap (armchair nanotubes remain metallic).[48] In theory, metallic nanotubes can carry an electric current density of 4 × 109 A/cm2, which is more than 1,000 times greater than those of metals such as copper,[49] where for copper interconnects current densities are limited by electromigration.
Because of their nanoscale cross-section, electrons propagate only along the tube's axis and electron transport involves quantum effects. As a result, carbon nanotubes are frequently referred to as one-dimensional conductors. The maximum electrical conductance of a single-walled carbon nanotube is 2G0, where G0 = 2e2/h is the conductance of a single ballistic quantum channel.[50]
There have been reports of intrinsic superconductivity in carbon nanotubes.[51][52][53] Many other experiments, however, found no evidence of superconductivity, and the validity of these claims of intrinsic superconductivity remains a subject of debate.[54]
پلی اکریلو نیتریل
قیر
پلی اکریلو نیتریل
قیر
purification:
The main impurities :graphite (wrapped up) sheets, amorphous carbon, metal catalyst and the smaller fullerenes…
Rules :-separate the SWNTs from the impurities
- give a more homogeneous diameter or size distribution.
The techniques that will be discussed are oxidation, acid treatment, annealing, ultrasonication, micro filtration, ferromagnetic separation, cutting, functionalisation and chromatography techniques.
Molecular-recognition AFM probe tips:
Certain bimolecular is attached to the CNT tip
This tip is used to study the chemical forces between molecules – Chemical force microscopy
Amyloid beta
disadvantage: Manual assembly method is time-consuming, needs proficient experimental technique, the fabrication yield is restricted.
Although water can pass through armchair
type SWCNTs with chiral vectors ranging between
(5,5) and (8,8), the diffusion of sodium ions is energetically
Transport of Small Molecules through CNTs.
Functionalization of the CNT end-groups, which are
the entrances to the CNT pores, can also be used to
influence the transport
too high for the smaller (5,5) and (6,6) SWCNTs.
However, these are all issues that are currently being addressed and altered for further advancements in the carbon nanotube field. The advantages of carbon nanotubes as nanovectors for drug delivery remain where cell uptake of these structures was demonstrated efficiently where the effects were prominent, showing the particular nanotubes can be less harmful as nenovehicles for drugs.[9] Also, drug encapsulation has been shown to enhance water dispersibility, better bioavailability, and reduced toxicity. Encapsulation of molecules also provides a material storage application as well as protection and controlled release of loaded molecule
Their intrinsic physicochemical features enable covalent and non-covalent binding of several pharmaceutical entities and allow for rational design of novel candidate nanoscale structures for drug development. CNTs can be functionalized with different functional groups to carry simultaneously several moieties for targeting, imaging and therapy.
It has been shown that small proteins can be entrapped
into the inner channel of opened nanotubes by simple adsorption
For in vivo applications, CNTs can be internalized
by cells, first by binding of their tips to
receptors on the cell membrane (86). This enables
transfection of molecular cargo attached to the
CNTwalls or encapsulated inside the CNTs (87).
For example, the cancer drug doxorubicin was
loaded at up to 60 wt % on CNTs compared with
8 to 10 wt % on liposomes (88). Cargo release can
be triggered by using near-infrared radiation
DNA sequencing: Nanotube fits into the major grove of the DNA strand
Apply bias voltage across CNT, different DNA base-pairs give rise to different current signals
With multiple CNT, it is possible to do parallel fast DNA sequencing
39387
39387
Products under development include inkjet–
printed test strips for estrogen and progesterone
detection, microarrays for DNA and protein
detection, and sensors forNO2 and cardiac troponin
(84). Similar CNTsensors have been used for gas
and toxin detection in the food industry, military,
and environmental applications (82, 85).
Single-walled carbon nanotubes (SWNTs) decorated with metal nanoparticles exhibit exquisite selectivity for adsorbing gas molecules. When the SWNT functions as the conduction channel in an electrical circuit, changes in the measured current can be used to detect gas adsorption and/or catalytic reactions at the SWNT surface. This approach has been used to develop an understanding of the interaction between metal nanoparticle decorated carbon nanotubes and a variety of gases, such as nitric oxide (NO), carbon monoxide (CO), hydrogen (H2), ammonia (NH3), nitrogen dioxide (NO2) and hydrogen sulfide (H2S) (refer to J. Phys. Chem. B., 2006 and Nano Lett., 2007).
39387
Products under development include inkjet–
printed test strips for estrogen and progesterone
detection, microarrays for DNA and protein
detection, and sensors forNO2 and cardiac troponin
(84). Similar CNTsensors have been used for gas
and toxin detection in the food industry, military,
and environmental applications (82, 85).
Single-walled carbon nanotubes (SWNTs) decorated with metal nanoparticles exhibit exquisite selectivity for adsorbing gas molecules. When the SWNT functions as the conduction channel in an electrical circuit, changes in the measured current can be used to detect gas adsorption and/or catalytic reactions at the SWNT surface. This approach has been used to develop an understanding of the interaction between metal nanoparticle decorated carbon nanotubes and a variety of gases, such as nitric oxide (NO), carbon monoxide (CO), hydrogen (H2), ammonia (NH3), nitrogen dioxide (NO2) and hydrogen sulfide (H2S) (refer to J. Phys. Chem. B., 2006 and Nano Lett., 2007).
were capable of increasing chromosome and DNA damage, and oxidative
stress in macrophage cell lines
Secondly, the CNTs are not homogenous
in their sizes (both diameters and lengths), which could be a problem for generation
of reproducible results that allows evaluation of the biological activity relating to specific
structures.
One major reason CNT devices have been so hard to scale up to industry uses is due to the inability to efficiently separate different species of CNT
Different types are produced randomly with 1/3 conducting 2/3 semiconducting
Ultra-centrifugation techniques (which are scale-able) are used to separate different CNT
Effective separation is seen
Separation according to metallicity
Separation according to diameter