“Nanoizing”
Mechanical Engineering
Nilanjan Mallik1, Wongdon Chu1, Gunjan Maheshwari1, Jandro Abot2, Albert Song2, Emily Head1, Mitul
Dadhania1, Vesselin Shanov1, Chaminda Jayasinghe1, Pravahan Salunke1, Lucy Lee1, Douglas Hurd1,
YeoHeung Yun1, Sergey Yarmolenko3, Jag Sankar3, Paul Phillips4, Richard A. Komoroski5, Wen-Jang
Chu5, Amit Bhattacharya5, Nelson Watts5, Mark J. Schulz1
1- NANOWORLD Lab and Smart Materials and Devices Lab, University of Cincinnati,
Cincinnati, OH 45221, Vesselin.Shanov@uc.edu, yunyg@email.uc.edu, Mark.J.Schulz@uc.edu
2-University of Cincinnati, Aerospace Engineering, Cincinnati, OH 45221
3-Department of Chemical and Mechanical Engineering, Center for Advanced Materials and Smart Structures,
North Carolina A&T State University, Greensboro, NC 27411
4-University of Cincinnati, Chemical and Materials Engineering, Cincinnati, OH 45221
5-University of Cincinnati, College of Medicine, Cincinnati, OH 45267
Cincinnati ASME Meeting
May 22, 2008
Outline
1. Benchmarking Nanoscale Materials
• Carbon Nanofibers (CNF), Carbon Nanotube
(CNT) Arrays, Carbon Nanosphere Chains
(CNSC), Carbon Nanotube Thread
• Ni Nanowires
2. Nanotechnology and Mechanical Engineering
• Nanomechanics (composites, sensors)
• Nanomedicine (biosensors, contrast agents)
• Other areas
3. Conclusions
UC Nanoscale Engineering
Supporters
•Carlo Montemagno
•Roy Eckart
•Stephen Kowel
•Frank Gerner
•Thomas Mantei
•Teik Lim
•Raj Singh
Nanoscale Engineering is Interdisciplinary
ASME
Benchmarking Carbon Nanoscale Materials
•Carbon Nanofibers (CNF)
from Applied Sciences Inc.
Advantages of CNF:
•high heat-transfer
•good strength
•good electrical conductivity
•low cost
Applied Sciences Pyrograf III material
•Carbon nanofibers (CNF) are multi-wall highly graphitic, low cost,
carbon fiber with diameters ranging from 70 to 200 nanometers and
a length from 50-100 microns.
•The walls are at an angle of about 20 degrees to the fiber axis and
terminate in a zig-zag form.
Benchmarking Carbon Nanoscale Materials
•Carbon Nanotube (CNT) Arrays
Carbon nanotubes
Substrate
CNT array with cm length are easy to handle, process, spin in
threads, cast in polymers, etc.
Carbon nanotube arrays are expected to have great applications in
nanomedicine, nanoelectronics , and nanocomposites
Substrate Design and Preparation is Critical for CVD
of CNT Arrays
Metal Catalyst
Si substrate
Al2O3
Thermal Annealing SiO2
Catalyst
Nanoparticles
Si substrate
CVD Growth
Carbon
Nanotubes
Si substrate
CVD Reactor at UC for Synthesis of CNT Arrays
T
C2H4(g) 2C(s) + 2H2(g)
H2
Chemical Vapor Deposition (CVD) of Carbon
Nanotubes – How Old is This Technique?
BC… UC
Production Scale Up: Manufacturing “Black CottonTM
with ET 3000 at UC”
NCATSU
Magnetron
Sputtering
In Situ Growth Observation of
the CNT Array During the CVD
Optical Images of a 18-mm Long Array of Aligned
CNTs
The UC Logo and the US Flag Written by CNT Arrays
Grown on Si (up: optical images, down: SEM images)
Characterization of CNT Arrays
ESEM (Environmental Scanning
Electron Microscopy): FEI XL-30
HRTEM (High Resolution Transmission
Electron Microscopy): JEOL JEM-2010
Micro-Raman Spectroscopy: LabRAM
HR
Thermo Gravimetric Analysis (TGA):
TA/TGA 2050
Thermal and Electrical Measurements
Keep counting, there should be 5
billion of them
Characterization of nanomaterials is
like detective work
High resolution image of MWCNT with 24 nm outer
diameter and 10 nm inner diameter
CNT Extraordinary Properties
High aspect ratio: length over diameter now ~106
High mechanical strength if no defects
Good electrical conductivity (metal or semiconductor)
Good thermal conductivity
Huge specific surface area (700 ft2/g SWCNT)
Can be functionalized to change their properties
Chemical stability
Benchmarking Carbon Nanoscale Materials
Carbon Nanosphere Chains (CNSC)
Grade I powder as grown Grade II material Grade III material
• Some amorphous • Post treated • Post treatment 1
carbon impurity • More graphitic for high electrical
conductivity
• Post treatment 2
for magnetic
properties
Unique Morphology Studied by ESEM
(a) (b)
The material consists of nanospheres interconnected in chains (a). This globular
structure is obvious at high magnification (b). The size of the spheres range from 60
to 90 nanometers. We refer to this material as CNSC (like multi-wall buckyballs)
Multi-plate collection Collection of the
chamber CNSC from one
plate
Multi-plate collection Collection from one plate
chamber
Packing CNSC in1 gallon jars after collecting the material
from the collection chamber.
Reaction chamber
CleanTech manufacturing facility with increased production capacity
(in operation 2007)
Single wall Carbon
Other Nanoscale Materials Nanotubes (SWCNT)
Barium titanate (BaTiO3)
ferroelectric nanotubes
Telescoping MWCNT Coiled made of oxide insulators
displacement sensor/actuator MWCNT Alloy nanowires
for pyroelectric and
piezoelectric sensors,
actuators
indium oxide ZnO nanowires ZnO nanowires arranged in ZnO nanobelts with
(In2O3) a sphere that may be an RF piezoelectric
nanowires receiver properties
Ni Nanowires at Different Magnification
• Strong magnetic properties
• High density
Nanomaterials- A challenge for engineers is to bring the properties of
nanomaterials to the macro scale
Carbon Atom Graphene Sheet Buckyball
•Angstrom size •Micron size in plane •Nanometer size
•Splitting requires high energy •High strength in plane •High strength
UC Effort
SW Carbon Nanotube
•Nanometer diameter, mm long
•High axial strength MWCNT CNT Tape and Thread
•Aligned, cm long •To spin or not to spin
http://www.ewels.info/img/science/graphite/index.html
•Strength and length
Nanomechanics: CNT Can be Spun into Thread
a)
b) c)
a) Spinning thread from long MWCNT arrays
b) Long CNT called “Black CottonTM” spun into thread may
provide reinforcement, sensing, and partial self-repair
simultaneously
c) Spun thread
Motor
Control
Board Slip Ring
Twisting Motor
Winding Motor
Winding Spool
CNT thread being twisted and drawn
CNT array holder
CNT array
Research setup for spinning CNTs into thread.
Spinning Nanotubes into Thread by
Industrial Nano (Brad Edwards)
Long carbon nanotubes called
“Black CottonTM” are being
used to spin thread which may
provide reinforcement, and CNT threads for body armor
sensing simultaneously http://news.bbc.co.uk/2/hi/science/nature/7038686.stm
Leaving the Planet by Space Elevator* Applications
CNT thread may form a
ribbon for a space elevator
*Reference: Leaving the Planet by
Space Space Elevator by Philip Ragan,
Elevator Bradley Edwards, published by
Lulu.com, 1/2006
Ribbon
(62,000 mi Composite Materials
long)
Developing Electrical Wire using CNT Thread
Goals are to understand electrical conduction in CNT Thread and optimize CNT
synthesis to produce spinnable CNT and then electrical wire
V vs I
2.50E-04
2.00E-04 y = 2.1483x + 1E-06
R2 = 0.9999
1.50E-04
Voltage (V)
1.00E-04
5.00E-05
AFRL WPAFB
0.00E+00
0.00E+00 2.00E-05 4.00E-05 6.00E-05 8.00E-05 1.00E-04 1.20E-04
Program Managers
-5.00E-05 •John Bulmer
Current (A) •Kevin Yost
Carbon Power Electronics
•Carbon nanosphere chains have high electrical
conductivity and weak magnetic attraction
(catalyst free) and may replace iron
•Carbon nanotube thread has electrical
conductivity and may replace copper
•Therefore, we are striving to demonstrate the
first all carbon electric motor
Magnetic pellet after Magnet attracting pellet Magnetic pellet movie
compressing CNSC
Optical Image of a 12 mm Thick Carpet of CNTs grown
on 4” Si
This sample proves that scaling up of the growth
process of super-long carbon nanotube arrays on large
area substrates is possible.
The feet of a Tokay gecko
which is native to South-East
Asia have about two million
densely packed, fine hairs, or
"setae", on each toe
Multiwalled carbon nanotube
hairs produced nanometer-
level adhesion forces 100
times higher than those
observed for gecko foot-hairs
Nanotube array fabric
with van der Waals
adhesion
http://en.wikipedia.org/wiki/Image:Smboxpsx.jpg
Short CNT Arrays for Woven Fabric Ply Reinforcement
(Jandro Abot of Aerospace Engineering)
Carbon Woven
MWCNT Array Fabric Ply
(a)
Bonded MWCNT Array (b)
Nanoreinforced Carbon
Woven Fabric Ply
(c)
a) MWCNT array attached to tape; b) nanoreinforced woven fabric
composite ply with the array bonded to the carbon woven fabric; c)
nanoreinforced laminated composite (NRLC)
Mechanical Testing of CNSC/Epoxy Nanocomposites
Displacement Transducer a b Steel Blocks P A c
A-A
Strain Gages
45°
Composite
Composite Specimen
Specimen
Roller
Load Cell 25 mm
Motor Shear Fixture P Threaded Bolts
Shear Test of the Nanocomposites using Iosipescu testing fixture
Epoxy Nanocomposite Sample Preparation
• Heavy duty shear mixer and tip
sonicator usage for dispersion of
CNSC in polymer matrix
• Curing the composites and casting
them in Aluminum and Teflon
molds depending on its
applications Mixing CNT and ultrasonication
Bottom Top
Mould Mould
Plasma system at UC made by Diener
Electronics, model PICO
Piezoresistive Properties of CNSC/Epoxy composites
Resistivity v/s Stress of a Nano Composite (2% CNSC & Epoxy)
40.00
Thousands)
(in
35.00
Resistivity (Ohms-centimeter)
30.00
25.00
20.00
15.00
10.00
5.00
0.00
1.46 2.91 4.37 5.83 7.28 8.74
Stress (MPa)
Pressure Sensor curve
Smart Nano Cement
Resistivity v/s Stress of a Nano Concrete (Sample II)
• Portland Cement mixed with
90
Series1
80
Carbon Nano Fibers (CNF) in 70
Resistivity(Ohms-cm)
Ball Milling Machine. 60
50
• Water is added in 40% weight 40
30
proportion. 20
• Paste is cast in a cylindrical mold 10
0
and piston. Heat is applied while 0 5 10
Stress(MPa)
15 20 25
curing
• Resistivity test is done and is F
found to be as low as 10 Ohms-
cms under pressure
• SHM Application: Can be used to
detect crack on concrete surface
F
Smart Nano Elastomer for SHM Application
• Polyurethane used as a base
material and CNSC dispersed in it
by means of DMF solvent
• The resulting film is very elastic
in nature and has good
mechanical properties.
• The film is electrically conductive
on one side and insulating on the
other side
• SHM Applications :
– Anti Icing Heater
– Erosion Resistance Coatings
– a low impedance piezoresistive
sensor
Smart Spray on Sensors for SHM Application
• A buckypaper spray of
CNSC/DMF and MWCNT/DMF
is sprayed on the fiber glass
composite beam.
• Beam is cured in vacuum and
plasma treated to improve the
bonding of spray on structure and
also improves the electrical
conductivity of the beam.
Smart Nano Ice for SHM Applications
• CNF when mixed with 2 drops
per 25 ml of DI water and frozen
in refrigerator gives Nano Ice as
shown in figure.
• Electrical characterization is done Nano Ice
as shown in the figure. The
resistance has been found out to
be in the range of 1.1 – 1.3 Mega
Ohms.
• Scrapping ability seems to be
getting coarser and more power is
needed to scrap the surface off.
Concept Smart Aircraft with Wings that Twist
NT Array Tower Grown at UC Nanotube Skin Actuator
Nanotube Post Actuator
Damage sensing and self-healing smart material
Piezoresistivity of fine CNT thread
9.4
9.2
Resistivity [10(-4) ohm-cm]
9
8.8
8.6
8.4
8.2
8
7.8
7.6
0 0.005 0.01 0.015 0.02 0.025 0.03
Strain
Spun CNT thread sensor with initial
average diameter of 30 microns and after
processing with a reduced diameter less
than 10 microns
Ref.
Nanomedicine Sensors, Devices
Nano-electronic sensors & in-body devices can detect disease
early and provide therapy when it is most effective
In Feb 2008 the inventor Ray Kurzweil said to BBC
that “(by 2029) machines and humans will eventually
merge through devices implanted in the body to boost
intelligence and health.” He said that in regard to
nanobots.
Questions for us.
How close are we to having nanobots?
What are the advances in nanoengineering so far?
What is coming in the future?
What are the most promising projects and lines of
investigation?
Image modified from NewScientist Magazine
MWCNT Tower Electrochemical Impedance Sensors
4 mm
MWCNT towers
Nanotube Tower
Tower cast in epoxy
with wire to form an
electrode Double-layer charge
Antibody (Ab)-Antigen (IgG) Binding
Redox probe, 5 mM of K3[Fe(CN)6],
K4[Fe(CN)6] in PBS solution (ph=7.0)
Increasing
frequency
(c)
(b)
(a)
EIS for IgG Ab-Ag testing, Dopamine sensing,
Glucose sensing, bone marker testing
On beating cancer (with nanotechnology)
Needed are the most advanced technologies and devices ever conceived by mankind
that will operate in the body to treat disease at the cellular and molecular levels.
Development of this new medicine will be a fantastic adventure that we are literally
betting our lives on.
8
(A) (B) Hundreds of (C) 10
cells over (d) (D)
sensor 6 (c)
Z mag (Ohm)
10
4
2 mm 10
(b)
channel (a)
Two 2
10 0 2 4 6
sensors 10 10 10 10
Freq (Hz)
Prototype micro-fluidic cell sensor array: (A) PDMS channel with two CNT sensors; (B) cells
in fluid channel; (C) cells flowing in channel; (D) magnitude plot of electrochemical
impedance in (a) HBSS; and with LNCap cells with different incubation times, (b) 5 min; (c)
20 min; (d) 2 hours. This test is with no antibody on the sensor.
Future implantable sensors built using nanotechnology
The “Nano da Vinci” Robot
The “da Vinci” Robot
SMART MATERIALS NANOTECHNOLOGY LAB
Concept Distributed Transponder Nanosensors for Asset Evaluation
and Data Mining on Composite Structures
NanoInductor Energy Density
5000
Energy Den (J/m^3)
Receiver 4000
Antenna
circuit 3000
Sensor and
2000
Super Transponder
capacitor 1000
Antenna 0
0 20 40 60 80 100
C Capacitive Current (micro-amp)
sensor
Predicted Energy density of a
nano-inductor solenoid/generator
Nanowire L
circuit
C
0sA/D
d/A
1 1
f 1.2GHz
2 LCeq
Concept Sensor (~ micron size) Electrical Model of CNT
Concept Nanoelectronic Brain Sensor
(Raj Narayan, Bill Ball)
Sensor, Needle to Polymer Coated
Electronics Si Inject Sensors MWCNT Coil Antenna
90µ
P
50µ L
Our intent is to develop the first nanoelectronic brain sensor that can be injected through an
intravascular approach or implanted percutaneously into the brain to continuously monitor key
physiological variables such as intracranial pressure. Length L for the antenna is TBD.
CNT grown on metal mesh shown at two magnifications for filtering blood, water, and air.
Development of CNT as Magnetic Resonance (MR) Imaging
Contrast Agents- Collaboration with the UC CIR at the COM
TE 175
ms
TE 175 ms
Varian INOVA 4T MRI system at
UC Center for Imaging Research
MRI Coil for Contrast Agent Research
Developed by Dr. Ron Pratt, Imaging
Research Center, Cincinnati Children's
Synthesize nanotubes with contrast agent inside
Hospital Medical Center
HRTEM images of CNT with encapsulated catalyst particles for MRI imaging.
Responsive Bioresorbable Mg Implants
(with North Carolina A&T SU, Univ. of Pittsburgh, Hannover Institute Germany)
0.5
Optional cathodic protection
Potential ( V vs Ag/AgCl )
0
& controlled release system
Battery -0.5
Responsive -1
(-)
Mg Implant
- -1.5
Electronically (+)
controlled - -2
Pt Anode
release of coating -2.5 -8 -6 -4 -2 0
- - Corrosion
10 10 10
2
Current ( A / cm )
10 10
rate, K1 Corrosion
Wireless bio-galvanic measurement using a
powered sensor
(-) Gamry Potentiostat
Mg ions
in solution
(+)
Pt Anode
Bone
regeneration
Biosafe high
Biodegradable
porous metal rate, K2 porosity implants
(F. Witte, Hannover
Inst. Germany)
Implant with options for
corrosion control & hydrogen
handling Nano-sensor array
Other Applications of CNT, CNSC, CNF, Ni NW
•Solar cells
•Fuel cell electrodes
•Lubricants in automobiles
•Fuel additive to improve gas mileage on cars?
•Carbon electronics (carbotronics)
•Aircraft drag reduction
•Firefighter garments
•Additive to water for fire suppression
•Radiation shielding
•Plant reinforcement (wood)
•Thermal sink electronics
•Electromagnetic flow of fluids using magnetic CNSC, Ni NW
UC Nanotechnology Education
New Courses New Edited Books
In Work: Unique Chapters
•Carbon Nanotube Sensors and
Electrodes, V K Varadan
•Medical Nanorobotics: The Long-Term
Goal for Nanomedicine by Robert A.
Freitas Jr.
•pRNA Nanomotor for Nanotechnology
and Gene Delivery by Peixuan Guo et al
•Mobile Microscopic Sensors for In-Vivo
Diagnostics by Tad Hogg
•Nanoscale Machines for Medicine by
Alex Zettl
Conclusions
•There are a very large number of materials combinations that can be tried to
synthesize nanoscale materials
•“Nanoizing” materials and structures is a new technological science that
Mechanical Engineers should pay attention to
•Think about improving structural performance and adding sensing at the same
time – sensing could be integrated within the material to make smart materials
•Interdisciplinary education is important to work in the NANOWORLD
•Nano-materials and intermediate products are generating intellectual property
and new entrepreneurial opportunities for creative engineers, small companies,
and universities.