Application of Nanotubes

E Antony

Common Applications

Field Emission (LED, etc)

Conductive plastics
Conductive adhesives & Connectors
Molecular electronics
Energy storage
Thermal materials (conduct or insulate)
Structural composites (Boeing 787,buildings,etc)
Catalytic & biomedical supports
others

What caught my interest?

The thermal similarity of the different types
of nanotubes and
The electrical differences between the
different types of nanotubes

Common Applications

Field Emission (LED, etc)

Conductive plastics
Conductive adhesives & Connectors
Molecular electronics
Energy storage
Thermal materials (conduct or insulate)
Structural composites (Boeing 787)
Catalytic & biomedical supports
others

Y?
I am interested in the relationship between
bonding, structure and properties of
substances.
So, why do the different forms have similar
properties in some cases but different
properties in other cases? These are
contrary to most substances which are
typically conductors of both heat and
electricity or neither.

Thoughts on what I wanted to develop

A tube which will conduct heat (sand) but

not electricity (colored sand) and a second
tube which will conduct both.
A means of relating these properties to the
molecular shapes.
A way of demonstrating at least one
application which uses these properties.

Designs
Tube 1 Zig-Zag
Consists of 2 nested PVC pipes each containing
straws which have been glued in place. The straws
are continuous between the two sets of pipes so that
in one position, sand can pass through easily
representing heat transfer. Rotation of the pipes
constricts the straws and prevents sand from passing
through easily-a semi-conductor. The pipes are of
different lengths such that the lower of the outer pipes
covers the lower inner pipe and a portion of the upper,
inner pipe.

Zig-Zag

Designs
Tube 2 Armchair
Like tube 1 except the straws have been cut
between the two sets of pipes so that rotation
of the pipes does not constrict the straws and
allows sand to pass through easily-a
conductor of heat or electricity. Again the
pipes are of different length such that the
lower of the outer pipes covers the lower inner
pipe and a portion of the upper, inner pipe.
Each pipe contains a diagram of the structure.

Armchair

Additional Visual Aids

Models of Zig-Zag and Armchair nanotubes have
been built using sp2 plastic models and
connectors. Along one side of each model, the
trigonal planar sp2 has been replaced with
trigonal bipyramidal sp3d with a plastic connector
attached to the outer axial position. This
demonstrates the position of the orbital involved
in pi bonding and allows the student to see why
the Armchair is well suited for electrical
conduction while the Zig-Zag is not.

Orbital Model Armchair

Orbital Model Armchair

Larger view Zig-Zag

Orbital Diagram Zig-Zag

An Introduction to Nanotubes

Open the website, https://www.ccs.uky.edu/~ernst/carbontubes/TubeApplet.html (this can be accessed through the Favorites
icon.
Move your cursor to the lower picture, click on the figure and practice rotating or otherwise manipulating the image. View the
tube from various perspectives so that you form a clear mental image of the structure.
The box labeled Nanotube Indices will allow you to change the type of nanotube being viewed as well as the size
(circumference) of the tube. You will notice that the default tube has indices (6,6). These indices are commonly referred to as
n and m (n,m). the default indices are typical of one type of tube, known as an armchair nanotube, where n=m. Try other
indices where n=m (suggestion, large values increase the calculation time so I would suggest using values of 4 to 20). I
would also suggest that you observe the tube with the open ends vertical. This will provide a consistent perspective to assist
you in seeing similarities and differences. What do the tubes have in common?
Repeat #3 using indices where m=0, i.e. (4,0), (7,0), etc. What do these have in common and how are they different from the
armchair tubes? These are known as zig zag nanotubes.
Repeat #3 using combinations where n is not equal to m or zero. These are known as chiral nanotubes. (I would suggest
using n values which are similar to m, although it is not necessary.)
Pick up the handout which was adapted from The Science Teacher and an overhead transparency showing a molecule of
graphene. Review the origin of the indices and how they describe the nanotube. Practice rolling the graphene overhead to
produce the nanotube structure.

Tube Identification and Labeling Activity

The previous computer activity helped you identify three different structures of carbon nanotubes (CNTs). This
activity will help clarify the labeling (indices) of the tubes.
You have before you a transparency with a model of a portion of a graphene molecule. Graphene is a single
sheet of graphite which we have looked at several times this year. A nanotube can be viewed as a rolled sheet of
graphene. There are three ways to do this create each by rolling your transparency sheet. Note that the direction
of the tube is shown by the direction of the cylinder being formed. Does this agree with what you saw on the
computer screen? If not, you may wish to return to the program and compare the figures.
For CNTs, the direction in which the graphene sheet is rolled can be identified by counting the number of carbon
atoms it takes to move to an equivalent position (see Figure 1 below). Since graphene is a 2 Dimensional lattice,
there are only 2 counting directions (identified as a 1 and a2) in which this can be done. Starting from an arbitrary
atom, the a1 and a2 vectors point toward the nearest equivalent atoms (Figure 1). The nanotube type is
determined by counting how many atoms in the a 1 direction (n) and how many in the a2 direction (m) are needed
to circumscribe the tube and return to the original position. Create a few CNTs using your transparency and
determine n and m for each. Then create the tube on the computer screen. Are the two images consistent?
(note that lengths will vary due to the number of cells shown on the screen). Compare your results to the figures
below

Figures and terminology for this sheet are from The Structures and Properties of Carbon, The Science Teacher,
Castellini, et.al, December 2006, Pages 36-41.

Figures for Tube ID and Zig Zag

Armchair

 Now return to the website. Focus on the graphic on the upper right side of the
display, specifically on the green lines. The green lines are directed along the
tube when the tube is aligned vertically. When one of these lines passes
directly through a vertex, the tube acts like a metal in that it is a conductor of
electricity. (We say that it is a metallic conductor. In fact it conducts much
better than a metal by a process called ballistic conductivity and is nearly a
superconductor.) However, when no line passes through a vertex, the tube is
a semiconductor, under what conditions is a tube metallic? (hint, use the
indices to systematically check out each type of tube) {your discoveries have a
solid basis in mathematics, but the math is beyond the scope of this course).
After you have reached your conclusions, we will demonstrate the phenomena.

Conductivity Demonstration

To demonstrate the thermal and electrical conductivity of the tubes you should have the two tubes and two containers of colored
sand available as well as vessels for collecting the sand as it is poured.

Starting with the Armchair model in the Thermal position, hold the tube over a receiving container and pour the sand.
(Comment-red hot, blue hot, etc) Note that the tube is an excellent conductor of heat. {Those interested in this process should
first read about phonons as the conductivity results from phonon waves)

Repeat the process with the Zig Zag model. Again, the nanotube is an excellent conductor of heat.

Now move the nanotube positions to Electrical and add the second color sand to the Armchair model. It is an excellent
conductor of electricity as well as heat.

Repeat the process with the Zig Zag model. Note that the electricity passes through but very slowly. Most Zig Zag tubes are
semiconductors.

At this point students may point out that, according to the computer animation, some of the Zig Zag tubes did conduct electricity.
Specifically those for which n/3 is a whole number are metallic. You should acknowledge that they are correct and that this
model, like all models, has limitations and that they just found one of them.

Assignment for day 2

Assignment for tomorrow: Reflect on possible applications of nanotubes. How could we use
them?

Investigate and be ready to report on an actual application on carbon nanotubes including:

What is the application?
What does that mean (provide a working definition, not a textbook definition).
What are the advantages provided by the nanotube compared to conventional materials?
Is the application based on the property investigated today? If not, what other useful property of
nanotubes was instrumental in their inclusion?
Citation of your source (Be thorough but you need not adhere to a particular format such as
APA).

Instructor Notes for Day 2

List some of the applications and summarize key properties of nanotubes based upon
the results of the student assignments.

Discuss why some of these are expected based upon the structure of the tubes.

Demonstrate the advantage of the fine tip using the demonstration device #2 and/or
the simplified model.

Show the images of the nanotube being used as the detecting tip on STM, AFM, etc
and as nanotweezers.

Demonstrations of the Importance of Tip Size

Demonstration # 1

This is a very simple demonstration yet it clearly shows the significance of tip size on probe sensitivity.

Preparation of materials

Using a material which is about 1/8 inch thick (Cardboard, stir stick for paint, etc), create an edge with an irregular
surface. This surface should have some slowly sloping areas and some narrow, deep (1/2 inch). Next, remove
the cap from a SharpieR pen and carefully cut off the closed end of the cap such that only the very tip of the pen
is exposed. Verify that it can write when in a vertical position.

Place a sheet of clean paper under the surface. Using the Sharpie R, trace along the edge of the surface. Place
the cut cap on the pen and again trace the surface. Show the results. It should be clear that the wide probe was
able to detect slow changes along the surface but could not provide significant information about crevices, etc,
while the fine tip yielded a much better representation of the surface.

Show the students the picture of the nanotube mounted on a conventional AFM tip (below). A picture of a folded
protein or similar structure would provide additional discussion for the class.

AFM tip with nanotube

Demonstration # 2

This demonstration shows both the significance of tip size and the magnification of a signal. This
magnification is mechanical as opposed to an instrument which uses electrical amplification.

Completing the Demonstration

Mount a pen in the Pen Holder and a fresh sheet of paper on the clipboard (our recording
device). Place the probe on the upper end of the surface to be scanned and slowly slide the
clipboard so that it pulls the sample upwards. You may have to relieve the tension if the probe
becomes stuck in one of the grooves in the sample. When the scan is complete, replace the
probe tip and repeat, preferably with a different color pen. Compare the two scans. Again, the
fine tip will yield a truer image and one with more detail. If you wish, you may measure the depth
of the crevices as well as the height of the peak it produced. Then compare the distance from
the fulcrum to the pen and from the fulcrum to the probe. Compare the two ratios. Discuss both
the advantages and disadvantages of magnification (a major disadvantage being the increase in
noise which is also evident in the trace).

Nanotweezers

Thank yous and Acknowledgements

Greta Zenner

Jen Ehrlich, Farrell Rogers and Sue Whitsett,

George Lisensky, Wendy Crone and Mike Condren

Katie Cadwell, Angela Johnson, Ken Gentry and Dana Horoszewski

Andrew Greenberg

Mark Eriksson and Ernst Richter