Carbon Nanomaterials Part 1

Dr. Virginia A. Davis Macroscale Assembly and Applications of Nanomaterials Spring 2013

Overview
Materials C60 and other fullerenes Carbon Nanotubes
Vapor grown carbon fiber, traditional carbon fiber
Graphene Other Structures

Topics Types Properties Production Techniques Functionalization

Fullerenes
A new family of carbon discovered in 1985 Closed Convex Carbon cage containing only hexagonal

and pentagonal faces

Carbon Chemistry
H H H - C - C-H H H What we all learned in high school

Resonance structure of graphite (stacked planes of carbon) Sp2 hybridization Fullerenes: The angle between a p axis and a C-C bond vector, is 101.6 (as compared to 90 in planar graphite) Concavity at each sp carbon center introduces strain but symmetry distributes the strain evenly across the structure http://www.chemistry.wustl.edu/~edudev/Fullerene/structure.html

ALLOTROPES OF CARBON

1 layer graphene

CARBON NANOTUBE/BUCKY BALL MODELS http://mrsec.wisc.edu/Edetc/pmk/pages/bucky.html CARBON NANOTUBE CONSTRUCTION

http://www.mrsec.wisc.edu/Edetc/modules/HighSchool/CNT_Vector_Activity/index.html

C60 Started it All

Discovered by Harold Kroto, James Heath, Sean O'Brien, Robert Curl, and

Richard Smalley in 1985 (Nature 318, 162).

1996 Nobel Prize in Chemistry went to Smalley, Kroto, Curl

If C60 was the size of a soccer ball the soccer ball would be the size of

Neptune
From one of Eulers theorem: spherical surface entirely built up from

pentagons and hexagons must have exactly 12 pentagons

Named Bucky-Ball after American Architect Buckminster Fueller who

designed geodesic domes

Many others C70, C78, C82, C84

12 pentagons arbitrary number of hexagons

Buckminster Fuller Time Magazine of January 10, 1964

http://www.fkf.mpg.de/andersen/fullerene/intro.html

Apparatus for Discovery C60

Vaporization laser beam strikes a rotating graphite disk plasma of vaporized carbon atoms. Pulsed nozzle passes high-density helium over the vaporization zone cooling the carbon atoms in the plasma and causing them to cluster and be carried through the apparatus Free expansion of the carbon cluster/gas mixture forms beam Beam is photoionized with a laser and detected by time of flight mass spectrometry Timing the laser firing and increasing the time between vaporization and expansion by adding integration cup resulted in stream resulted in predominantly C60 with some C70 http://www.chemistry.wustl.edu/~edudev/Fullerene/discovery.html

C60 Potential Applications

Biopharmaceutical ( C

Sixty Inc)
Free radical Sponge Buckysomes targeted

drug delivery
Pre-clinical trials in progress

Catalysts Electronics Packaging Molecular Devices Polymer Additive Dye (Blacker than
ROS = Reactive Oxygen Species http://www.csixty.com/antioxidant.html

Carbon Black)
Polymer-Solar Cells: C60

good for charge transfer

Nano- To Micro- Scale Properties Of SWNTS

Electrical conductivity similar to copper (metallic SWNTs) ballistic conductance, 1 cm at 25 oC (McCuen, 2002) Thermal conductivity equal or better than that of diamond ~ 3000 W / m K (Hone, 2000) Low density, small size density ~ 1.4 g/cm3 , packing ~ 1x1014 SWNT/cm2 Strongest known natural or synthetic material, 100x stronger and 6x lighter than steel tensile strength at least 37 GPa and strain to failure at least 6 % (Walters et al. 1999; Yu et al. 2000) Youngs modulus ~ 0.62 to 1.25 TPa (Gao et al. 1998; Krishnan et al. 1998; Yu et al. 2000)

CAN THESE PROPERTIES BE REALIZED IN A MACROSCOPIC SYSTEM???????????

Ways to Think of Nanotubes

Chemist
Single element polymer C1,000,000 and

beyond

Physicist
Single Crystal

Civil Engineer
Beam and Truss

Yakobson and Smalley

SINGLE-WALLED CARBON NANOTUBES (SWNTs)

Discovered by Iijima in 1991 Rolled sheet of graphite Vector Ch defines diameter, chirality and properties

n=5 m=0

C h na 1 m a 2 d Ch

0.142 nm a i = 1.42 nm

Ballistic conductor n-m = 0 Metal or Very Small band gap semiconductor: n m integer divisible by 3 Semiconductor: n - m not zigzag divisible by 3 Zigzag: (0,m) or (n,0)

Dresselhaus and Avouris 2001

SINGLE-WALLED CARBON NANOTUBES (SWNTs)

Discovered by Iijima in 1991 Rolled sheet of graphite Vector Ch defines diameter, chirality and properties

n =5

m=5

C h na 1 m a 2 d

Ch

ai = 1.42 nm 0.142 nm*

Ballistic conductor n-m = 0 Metal or Very Small band gap semiconductor: n m integer divisible by 3 Semiconductor: n - m not zigzag divisible by 3 Zigzag: (0,m) or (n,0) Armchair: (n,m) n = m armchair

Dresselhaus and Avouris 2001

SINGLE-WALLED CARBON NANOTUBES (SWNTs)

Discovered by Iijima in 1991 Rolled sheet of graphite Vector Ch defines diameter, chirality and properties

n=7

C h na 1 m a 2 d Ch

m=3 (n,m) : (7,3) chiral semiconductor

0.142 nm a i = 1.42 nm

Ballistic conductor n-m = 0 Metal or Very Small band gap semiconductor: n m integer divisible by 3 Semiconductor: n - m not divisible by 3 zigzag Zigzag: (0,m) or (n,0) Armchair: (n,m) n = m Chiral: (n,m) n m

armchair chiral

Dresselhaus and Avouris 2001

Why Bonding (Electronic Structure) Controls Electrical Properties

Valence band: highest range of electron energies occupied at absolute zero Conduction band: Electron energies at which electrons can accelerate under applied electron field creating current Semiconductor: At room temp some electrons can overcome the BAND GAP and enter conduction band, typically < 3 eV (1 eV = 1.602 x 1019 J ) Metal: conduction and valence bands overlap: Zero band gap http://en.wikipedia.org/wiki/Conduction_band

SWNTs Are Anisotropic

RAJAT DUGGAL (former grad student now employed by GE) 22 April 2005, Guinness World Record Model of a 5-5 Single Walled Carbon Nanotube (SWNT) ~65,000 pieces 360 m long, 0.36 m wide (L/D = 1000) about 100 builders over 1000 in attendance Supremely Silly (from Rick Smalley)

Types of Carbon Nanotubes (CNTs)

BEWARE OF TERMINOLOGY !!!!!!!!!!!!!!!!!

CNT is a general term not a specific entity Gorillas, chimpanzees, and orangutans are all apes, but have vastly different characteristics Apples to Oranges Comparisons Abound in

the Peer Reviewed Literature and Popular Press

VGCF
Vapor Grown Carbon Fiber (VGCF) Highly imperfect, not exactly even a carbon nanotube Much bigger can be > 100 nm diameter Much easier to disperse than SWNTs or MWNTs Much lower aspect ratio Much Cheaper Worse properties on nanoscale Sometimes used for method development prior to using

SWNTs, but there are dramatic differences in how they process

SWNTs
SWNTs molecular perfection Dimensions, chiralities, defects vary widely depending on production and purification processes All sp2 Hybridized carbons Ends more reactive due to strain and endcaps often lost during purification Molecular perfection makes them hard

to disperse
500 eV/micron van der Waals attraction

Bundle of SWNTs Spaces between lines (circle diameter) ~ 1 nm

5 m
http://cohesion.rice.edu/naturalsciences/smalley/emplibrary/ropes_1d.jpg Davis et al 2004

MWNTs/FWNTs/DWNTs
MWNTs Multi-Walled Carbon Nanotubes (MWNTs) Like nested SWNTs Easier to disperse Quality & dimensions vary widely If 2 cylinders: Double Walled Carbon Nanotubes (DWNTs) If a few cylinders: FWNTs
1 MWNT

Courtesy Huina Guo & Dr. Satish Kumar, GaTech

WHAT ARE POTENTIAL APPLICATIONS OF SWNTS???

WHAT ARE THE OBSTACLES??? HOW DO YOU SYNTHESIZE CARBON NANOMATERIALS??