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NATO LECTURES
M. Meyyappan

Nanotechnology in Aerospace Applications

Abstract

The aerospace applications for nanotechnology include high strength, low weight
composites, improved electronics and displays with low power consumption, variety of
physical sensors, multifunctional materials with embedded sensors, large surface area
materials and novel filters and membranes for air purification, nanomaterials in tires
and brakes and numerous others. This lecture will introduce nanomaterials particularly
carbon nanotubes, and discuss their properties. The status of composite preparation –
polymer matrix, ceramic matrix and metal matrix – will be presented. Examples of
current developments in the above application areas, particularly physical sensors,
actuators, nanoelectromechanical systems etc. will be presented to show what the
aerospace industry can expect from the field of nanotechnology.

Of all the nanoscale materials, carbon nanotubes (CNTs) have received the most attention
across the world. These are configurationally equivalent to a two-dimensional graphene
sheet rolled up into a tubular structure. With only one wall in the cylinder, the structure
is called a single-walled carbon nanotube (SWCNT). The structure that looks like a
concentric set of cylinders with a constant interlayer separation of 0.34 A is called a
multiwalled carbon nanotube (MWCNT).

The CNT’s structure is characterized by a chiral vector (m, n). When m-n/3 is an integer,
the resulting structure is metallic; otherwise, it is a semiconducting nanotube. This is a
very unique electronic property that has excited the physics and device community

Meyyappan, M. (2007) Nanotechnology in Aerospace Applications. In Nanotechnology Aerospace Applications – 2006 (pp. 7-1 – 7-2).
Educational Notes RTO-EN-AVT-129bis, Paper 7. Neuilly-sur-Seine, France: RTO. Available from: http://www.rto.nato.int/abstracts.asp.

RTO-EN-AVT-129bis 7-1
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Nanotechnology in Aerospace Applications

leading to numerous possibilities in nanoelectronics. CNTs also exhibit extraordinary

mechanical properties. The Young’s modulus is over 1 TPa and the tensile strength is
about 200 GPa. The thermal conductivity can be as high as 3000 W/mK. With an ideal
aspect ratio, small tip radius of curvature and good emission properties, CNTs also have
proved to be excellent candidates for field emission. CNTs can be chemically
functionalized, i.e. it is possible to attach a variety of atomic and molecular groups to the
ends of sidewalls of the nanotubes.

The impressive properties alluded above have led to investigations of various

applications. The most important aerospace application is high strength, low weight
composites. Investigation of metal and ceramic matrix composites with CNTs as a
constituent materials is in its infancy. A status update will be provided. CNTs have been
shown to provide desirable electrical properties for polymer matrix composites. In many
cases, the current problem is the inability to disperse the nanotubes homogeneously
across the host matrix.

Other applications for CNTs include electronic components, logic and memory chips,
sensors, catalyst support, adsorption media, actuators, etc. All early works in
nanoelectronics use CNTs as a conducting channel in an otherwise silicon CMOS
configuration. This approach may not really have a future as the use of CNTs, while
inherently not solving any of the serious problems of CMOS downscaling (such as
lithography, heat dissipation, etc.), it doesn’t show an order of magnitude performance
improvement either. The critical issue now is to develop alternative architectures in
addition to novel materials. In contrast, the opportunities for CNTs in sensors – both
physical and chemical sensors – are better and near-term.

The opportunities for aerospace industry are through thermal barrier and wear resistant
coatings, sensors that can perform at high temperature and other physical and chemical
sensors, sensors that can perform safety inspection cost effectively, quickly, and
efficiently than the present procedures, composites, wear resistant tires, improved
avionics, satellite, communication and radar technologies.

7-2 RTO-EN-AVT-129bis
M. Meyyappan
• High Strength Composites (PMCs, CMCs, MMCs…)

• Nanostructured materials: nanoparticles, powders, nanotubes…

• Multifunctional materials, self-healing materials

• Sensors (physical, chemical, bio…)

• Nanoelectromechanical systems

• Batteries, fuel cells, power systems

• Thermal barrier and wear-resistant coatings

• Avionics, satellite, communication and radar technologies

• System Integration (nano-micro-macro)

• Bottom-up assembly, impact of manufacturing

• Processing them into various matrices follow earlier composite
developments such as
- Polymer compounding
- Producing filled polymers
- Assembly of laminate composites
- Polymerizing rigid rod polymers
-
-

• Purpose
- Replace existing materials where properties can be superior
- Applications where traditionally composites were not a
candidate
• Nanotechnology provides new opportunities for radical changes
in composite functionality

• Major benefit is to reach percolation threshold at low volumes

(< 1%) when mixing nanoparticles in a host matrix

• Functionalities can be added when we control the orientation

of the nanoscale reinforcement.
• This always implies “structure +” since in most cases the major
function of a structure is to carry load or provide shape.
Additional functions can be:
• Actuation controlling position, shape or load
• Electrical either insulate or conduct
• Thermal either insulate or conduct
• Health monitor, control
• Stealth managing electromagnetic or visible signature
• Self-healing repair localized damage
• Sensing physical, chemical variables NRC Report, 2003
• Building in additional functionalities into load-bearing structures
is one key example:
- Sensing function
* Strain
* Pressure
* Temperature
* Chemical change
* Contaminant presence
• Miniaturized sensors can be embedded in a distributed fashion to
add “smartness” or multifunctionality. This approach is ‘pre-nano’
era.
• Nanotechnology, in contrast, is expected to help in assembling
materials with such functional capabilities
• Possible, in principle, to design any number of composites with multiple levels
of functionality (3, 4, 5…) by using both multifunctional matrices and
multifunctional reinforcement additives

- Add a capsule into the matrix that contains a nanomaterial sensitive to

thermal, mechanical, electrical stress; when this breaks, would indicate the
area of damage

- Another capsule can contain a healant

- Microcellular structural foam in the matrix may be radar-absorbing,

conducting or light-emitting

- Photovoltaic military uniform also containing Kevlar for protection

generate power during sunlight for charging the batteries of
various devices in the soldier-gear
NRC Report, 2003
• Carbon nanotubes, nanofibers

• Polymer clay nanocomposites

• Polymer cross-linked aerogels

• Biomimetic hybrids

Expectations:
- ‘Designer’ properties, programmable materials
- High strength, low weight
- Low failure rates
- Reduced life cycle costs
 ‘Self-healing plastic’ by Prof. Scott White (U. of Illinois)
Nature (Feb. 15, 2001)
• Plastic components break because of mechanical or thermal
fatigue. Small cracks ⇒ large cracks ⇒ catastrophic failure.
‘Self-healing’ is a way of repairing these cracks without human
intervention.
• Self-healing plastics have small capsules that release a healing
agent when a crack forms. The agent travels to the crack
through capillaries similar to blood flow to a wound.
• Polymerization is initiated when the agent comes into contact
with a catalyst embedded in the plastic. The chemical reaction
forms a polymer to repair the broken edges of the plastic. New
bond is complete in an hour at room temperature.
• Plasma processing
- Both thermal (plasma arc, plasma torch, plasma spray) and
low temperature (cold) plasma are used
• Chemical Vapor Deposition
- Either on a substrate or in the gas phase (for bulk production)
- Metallic oxides and carbides
• Electrodeposition
• Sol-gel processing
• Ball mill or grinding (old fashioned top-down approach)

Key Issue: Agglomoration

Tremendous increase in surface-to-volume ratio

• Increase in solubility

• Increase in reactivity

• Possible increase in hardness (ex: titanium nitride)

Application range is wide as seen in the next two tables.

 Source: Wilson et al 2002

MARKET PARTICLES REQUIRED NANOTECHNOLOGY ADVANTAGES

Polishing Slurries Aluminum Oxide Faster rate of surface removal reduces
operating costs
Cerium Oxide Less material required due to small size of
particles
Tin Oxide Better finishing due to finer particles
Capacitors Barium Titanate Less material required for a given level of
capacitance
Tantalum High capacitance due to reduction in layer
thickness and increased surface area resulting
from smaller particle size

Alumina Thinner layers possible, thus significant potential

for device miniaturization
Pigments Iron Oxide Lower material costs, as opacity is obtained with
smaller particles
Zirconium Silicate Better physical-optical properties due to
Titanium Dioxide enhanced control over particles

Dopants Wide variety of materials Improved compositional uniformity

required depending on Reduction in processing temperature reduces
application operating and capital costs
 Source: Wilson et al 2002

MARKET PARTICLES REQUIRED NANOTECHNOLOGY ADVANTAGES

Structural Ceramics Aluminium Oxide Improved mechanical properties

Aluminium Titanate Reduced production costs due to lower
sintering temperatures
Zirconium Oxide

Catalysts Titanium Dioxide Increased activity due to smaller particle

size

Cerium Oxide Increased wear resistance

Alumina

Hard Coatings Tungsten Carbide Thin coatings reduce the amount of

material required
Alumina

Conductive Inks Silver Increased conductivity reduces

consumption of valuable metals
Tungsten Lower processing temperatures
Nickel Allows electron lithography
CNT is a tubular form of carbon with diameter as small as 1 nm.
Length: few nm to microns. See textbook on
Carbon Nanotubes:
CNT is configurationally equivalent to a single or multiple two Science and
dimensional graphene sheet(s) rolled into a tube (single wall vs. Applications,
multiwalled). M. Meyyappan,
CRC Press, 2004.

CNT exhibits extraordinary mechanical

properties: Young’s modulus over
1 Tera Pascal, as stiff as diamond, and tensile
strength ~ 200 GPa.

CNT can be metallic or semiconducting,

depending on (m-n)/3 is an integer (metallic)
or not (semiconductor).
• The strongest and most flexible molecular material because of C-C
covalent bonding and seamless hexagonal network architecture

• Strength to weight ratio 500 time > for Al, steel, titanium; one
order of magnitude improvement over graphite/epoxy

• Maximum strain ~10% much higher than any material

• Thermal conductivity ~ 3000 W/mK in the axial direction

with small values in the radial direction

• Very high current carrying capacity

• Excellent field emitter; high aspect ratio and small

tip radius of curvature are ideal for field emission

• Can be functionalized
• CNT has been grown by laser ablation
(pioneered at Rice) and carbon arc process
(NEC, Japan) - early 90s.
- SWNT, high purity, purification methods
• CVD is ideal for patterned growth
(electronics, sensor applications)
- Well known technique from
microelectronics
- Hydrocarbon feedstock
- Growth needs catalyst
(transition metal)
- Growth temperature
500-950° deg. C.
- Numerous parameters
influence CNT growth
- Surface masked by a 400 mesh TEM grid
- Methane, 900° C, 10 nm Al/1.0 nm Fe

Delzeit et al., Chem. Phys. Lett.,

348, 368 (2001)
 - Surface masked by a 400 mesh TEM grid;
20 nm Al/ 10 nm Fe; 10 minutes

Grown using ethylene at 750o C

Delzeit et al., J. Phys. Chem. B, 106, 5629 (2002)
• Certain applications such as nanoelectrodes, biosensors would
ideally require individual, freestanding, vertical (as opposed to
towers or spaghetti-like) nanostructures

• The high electric field within the sheath near the substrate in a plasma
reactor helps to grow such vertical Cassell et al., Nanotechnology, 15 (1), 2004
structures

• dc, rf, microwave, inductive

plasmas (with a biased substrate)
have been used in PECVD of
such nanostructures
• Needed for composites, hydrogen storage, other applications
which need bulk material
• Floating catalysts (instead of supported catalysts)
• Carbon source (CO, hydrocarbons)
• Floating catalyst source (Iron pentacarbonyl, ferrocene…)
• Typically, a carrier gas picks up the catalyst source and goes
through first stage furnace (~200° C)
• Precursor injected directly into the 2nd stage furnace
• Decomposition of catalyst source, source gas pysolysis, catalyzed
reactions all occur in the 2nd stage
• Products: Nanotubes, catalyst particles, impurities
• Carbon nanotubes viewed as the “ultimate” nanofibers ever made
• Carbon fibers have been already used as reinforcement in high strength, light
weight, high performace composites:
- Expensive tennis rackets, air-craft body parts…
• Nanotubes are expected to be even better reinforcement
- C-C covalent bonds are one of the strongest in nature
- Young’s modulus ~ 1 TPa ⇒ the in-plane value for defect-free graphite
• Problems
- Creating good interface between CNTs and polymer matrix necessary
for effective load transfer
WHY?

œ CNTs are atomically smooth; h/d ~ same as for polymer chains

 CNTs are largely in aggregates ⇒ behave differently from individuals
• Solutions
- Breakup aggregates, disperse or cross-link to avoid slippage
- Chemical modification of the surface to obtain strong interface with
surrounding polymer chains
• Polymer matrix composites
- Nanotube dispersion
- Untangling
- Alignment
- Bonding
- Molecular Distribution
- Retention of neat-CNT properties

• Metal and Ceramic Matrix Composites

- High temperature stability
- Reactivity
- Suitable processing techniques
- Choice of chemistries to provide stabilization and bonding
to the matrix.
• High aspect ratio allows percolation at lower compositions than spherical fillers
(less than 1% by weight)

• Neat polymer properties such as elongation to failure and optical transparency

are not decreased.

• ESD Materials: Surface resistivity should be 1012 - 105 Ω/sq

- Carpeting, floor mats, wrist straps, electronics packaging

• EMI Applications: Resistivity should be < 105 Ω/sq

- Cellular phone parts
- Frequency shielding coatings for electronics

• High Conducting Materials: Weight saving replacement for metals

- Automotive industry: body panels, bumpers (ease of painting without a
conducting primer)
- Interconnects in various systems where weight saving is critical
E.V. Barrera, Rice University in Carbon Nanotubes: Science and Applications: M. Meyyappan, CRC Press, 2004
E.V. Barrera, Rice University in Carbon Nanotubes: Science and Applications: M. Meyyappan, CRC Press, 2004
• More & more components are packaged in smaller spaces where electromagnetic
interference can become a problem
- Ex: Digital electronics coupled with high power transmitters as in many
microwave systems or even cellular phone systems

• Growing need for thin coatings which can help isolate critical components from
other components of the system and external world

• Carbon nanofibers have been tested for EMI shielding; nanotubes have potential
as well
- Act as absorber/scatterer of radar and microwave radiation
- High aspect ratio is advantageous
- Efficiency is boosted by small diameter. Large d will have material too
deep inside to affect the process. At sub-100 nm, all of the material
participate in the absorption
- Carbon fibers and nanotubes (< 2 g/cc) have better specific conductivity
than metal fillers, sometimes used as radar absorbing materials.
 Single Wall Carbon Nanotube

• Every atom in a single-walled nanotube (SWNT) is on

the surface and exposed to environment
• Charge transfer or small changes in the charge-
environment of a nanotube can cause drastic changes
to its electrical properties
 Sensor fabrication:
1. SWCNT dispersions--Nice dispersion of CNT in DMF
2. Device fabrication--(see the interdigitated electrodes below)
3. SWCNT deposition—Casting, or in-situ growth

Jing Li et al., Nano Lett., 3, 929 (2003)

 • Sensor tested for NO2, NH3,
acetone, benzene, nitrotoulene…
• Test condition:
Flow rate: 400 ml/min
Temperature: 23 oC
Purge & carrier gas: N2
• Sensitivity in the ppb range
• Selectivity through (1) doping,
(2) coating CNTs with polymers,
(3) multiplexing with signal
processing

Detection limit for NO2 is 44 ppb.

• Need more work to speedup
recovery to baseline
• Electronic properties are independent
of helicity and the number of layers

• Applications: Nanoelectronic devices,

composites

• Techniques: Arc discharge,

laser ablation

• Also: B2O3 + C (CNT) + N2 → 2 BN

(nanotubes) + 3 CO
 (INWs)

• All these have been grown as 2-d

thin films in the last three decades
• Current focus is to grow 1-d
nanowires

Motivation

• One-dimensional quantum
confinement
• Bandgap varies with wire diameter
• Single crystal with well-defined
surface structural properties
• Tunable electronic properties
by doping
• Truly bottom-up integration
possible

V.S. Vavilov (1994)

Down to 0.4 eV
(0001)
 25

figure of merit, ZT
Low dimensional systems
nanowires 20
9 Conduction electron density of 15
state À
9 Seebeck coefficient À 10
n-doped
9 Structural constraints p-doped
5
thermal conductivity ¾
*PRL 47, 16631 (1993) 0
0 10 20 30
wire width (nm)
MATERIAL APPLICATION
Silicon Electronics, sensors
Germanium Electronics, IR detectors
Tin Oxide Chemical sensors
Indium Oxide Chemical sensors, biosensors
Indium Tin Oxide Transparent conductive film in display electrodes, solar
cells, organic light emitting diodes
Zinc Oxide UV laser, field emission device, chemical sensor
Copper Oxide Field emission device
Wide Bandgap Nitrides (GaN) High temperature electronics, UV detectors and lasers,
automotive electronics and sensors
Boron Nitride Insulator
Indium Phosphide Electronics, optoelectronics
Zinc Selenide Photonics (Q-switch, blue-green laser diode, blue-UV
photodetector)
Copper, Tungsten Electrical interconnects
• Nanotechnology is an enabling technology that will impact the aerospace
sector through composites, advances in electronics, sensors,
instrumentation, materials, manufacturing processes, etc.

• The field is interdisciplinary but everything starts with material science.

Challenges include:
- Novel synthesis techniques
- Characterization of nanoscale properties
- Large scale production of materials
- Application development

• Opportunities and rewards are great and hence, there is a tremendous

worldwide interest