Practical Use of

Nanomaterials in Plastics
Innovative Technologies
Symposium for Plastics
J uly 31, 2007
J oseph J . Schwab
www.hybridplastics.com
Hybr i d

Pl ast i c s
What is Nanotechnology?
!Nanotechnology is the understanding and control
of matter at dimensions of roughly 1 to 100
nanometers.
!Nanotechnology involves imaging, measuring,
modeling, and manipulating matter at this length
scale.
!At the nano-scale, the physical, chemical, and
biological properties of materials differ from the
properties of individual atoms and molecules or
bulk matter, creating improved materials,
devices, and systems that exploit these new
properties.
What is Nanotechnology?
A hundred years ago, or even fifty,
nanotechnology would have just been
called chemistry
Economist, 5 July 2001
What is Nanotechnology?
Nanotechnology
Nanodevices
Molecular
Electronics
Mems &
BioMems
Lab on Chip
Sensors &
Detectors
Device
Miniaturization
Nanotools
Fabrication
Techniques
Instrumentation
Metrology &
Analysis
Software
Computation
Simulation
Nanostructured
Materials
Nanoparticles
Supramolecular
Assemblies
Nanocomposites
Representative Types of Nanoparticles
Nanoparticles
Carbon Tubes
-Single Walled
-Multi Walled
Fullerenes
Clays
-Montmorillonite
-Halloysite
-Vermiculite
Metal & Metal Oxides
Silica
POSS

-Molecular Silicas
-Monomers
-Silanols
-Polymers
Nanofibers
Dendrimers
Graphenes
1 mm
0.1 nm
1.0 nm
10 nm
100 nm
1 !m
100 !m
10 !m
Sewing Needle
Razor Blade Thickness
Human Hair
Most Cells & Fibers
Bacteria, Fillers &
Polymer Morphology
Viruses & Nanofillers
Macromolecules
POSS

Building Blocks
Atoms / Small Molecules
0.1-10 nm Defect Nucleation
1-10 nm Critical Nucleus Size
1-10 nm Surface Corrugation
0.5-50 nm Chain Motion Therm-Mech.
1-1000 nm Dislocation Interaction Mechanics
1-100 nm Crack Tip Radius
10-50 nm Entanglement Rad.
0.1-10 nm Primary Structure Polymers
10-1000 nm Secondary Structure
1-100 nm Quantum Well Optical
10-1000 nm Wave Decay
1-100 nm Tunneling Electronics
0.1-5 nm Porosity Control Membranes
1-100 nm Cell Walls Biology
1-10 nm Surface Topology Catalysis
Critical Length Property Field
Why is Nano Important in Materials?
Nanomaterials Are Really Not New
What has been, that will be; what has been done, that will be done.
Nothing is new under the sun. Even the thing which we say, See, this
is new! has already existed in the ages that proceeded us.
Ecclesiastes 1, 9-10



Source: University of Dayton NEST Lab
Carbon Nanotubes
Source:Wikimedia Commons
Source:Peter Harris
Source:Peter Harris
Multi-walled Nanotubes
Source:Hyperion Catalysis
Source:Hyperion Catalysis
Source:Hyperion Catalysis
Carbon Nanotubes
Carbon Nanotubes (CNTs) typically have diameters 1000
times smaller than traditional carbon fibers.
Single-walled CNTs (SWCNTs) consist of a single tubular
graphene sheet and have diameters of 1-2nm.
Multi-walled CNTs (MWCNTs) typically consist of 5-15
tubular graphene layers and have diameters of 10-12nm.
CNTs can be up to 50 times stronger than steel and have
excellent thermal and electrical conductivity.
Fullerenes
RO OR
O O
C
60
Fullerene
Chemically Modified C
60
Fullerene
Endohedral
C
60
Fullerene
Timeline for Fullerenes
(A Cautionary Tale)
In 1985 C
60
is discovered. By 1990 a process for making gram quantities is developed and accelerates
research efforts.
At the end of 2001 Mitsubishi Chemical Corporation and Mitsubishi Corporation establish a joint venture
called the Frontier Carbon Corporation (FCC) with the goal of becoming the world leader in the
commercial production of nano-scale carbon products.
In 2002 FCC claims mass production of 400kg/yr of fullerenes.
By 2003 FCC claims to be operating a 40 tons/year commercial-scale, low-cost plant to produce
fullerenes. FCC claims delivery of fullerene samples at prices ten times lower than 2002 prices. FCC
also claims first commercial product, a bowling ball.
In 2004 FCC claims 400 J apanese companies have purchased samples. Claims that commercial
products in J apan include fiber reinforced composites for badminton rackets, tennis rackets, golf club
shafts, snow boards, ski and snow board wax, lubricants for car air conditioners, and coatings for glass.
In December 2004 FCC establishes Frontier Carbon Corporation of America (FCCA) To meet the
growing commercial demand for nano-scale products in the United States and Europe. FCCA is to
begin production of fullerene materials in the U.S.
In 2005 FCCA announces an agreement with TDA Research to offer a range of fullerene products under
the Nanom product line.
Although many claims about mass production, costs remain high.
Nanoclay

Source:Wikimedia Commons


Source:Southern Clay
Source:Natural Nano
Nanoclay
Almost all nanoclays used in the plastics industry
are minerals which are mined from naturally
occurring deposits.
Montmorillonite is the most widely used clay. It
has a plate-like anisotropic structure and is nano
in only one dimension.
Halloysite is a tube shaped clay having a typical
diameter of 40-200nm and a length of 0.5-10um.
Metal & Metal Oxide Nanoparticles

Source:Nanophase Technologies
Source:Nanophase Technologies
Source:Nanophase Technologies
Metal oxide nanoparticles are actually isolated as
agglomerates, typically over 1,000 nanometers in
size, and behave similarly to conventional powders.
POSS

Nanostructures
One or more reactive
groups for grafting or
polymerization.
Thermally and chemically
robust hybrid
(organic-inorganic)
framework.
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
X
Nanoscopic size
Si-Si distance = 0.5 nm
R-R distance = 1.5 nm.
Precise three-dimensional structure for
molecular level reinforcement of polymer
segments and coils.
Unreactive organic (R)
groups for solubilization
and compatibilization.
Si
Si
O
O
Si
Si Si
O
O
OH
OH
Si
O
Si
O
O
O
O
OH
R
R
R
R
R
R
R
Stable Silanols
Si
Si
O
O
Si
Si
M
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
Metal Containing
Why Should We Expect Improvements?
A unique aspect of nanotechnology is the vastly increased ratio of surface
area to volume present in many nano-scale materials.
Nanoparticles in particular have a very high surface area to volume ratio.
For example, montmorillonite nanoclay platelets have a surface area of
750 m
2
/g. This means that ~7g of platelets could cover an area the size
of a football field.
This enormous surface means that in a nanocomposite almost all of the
matrix (polymer) will be in contact with the nanoparticle.
Since the physical properties of the nanoparticles themselves are
generally superior to the polymer matrix this suggests that the properties
of the nanocomposite will trend toward those of the nanoparticle.
Keys to Nanocomposite Polymers
Compatibility: Nanoparticle must have compatibility with matrix.
Dispersion: If good compatibility is achieved, complete dispersion at the
molecular/nano level should occur.
Properties: If dispersion at the molecular/nano level is achieved, improved
optical, physical and mechanical properties should result.
Compatibility ! Dispersion ! Improved Properties
Unfortunately nanoparticles are rarely compatible with polymer matrices
and a tremendous amount of time, money, and effort has gone into trying
to overcome this problem. If the nanoparticle is not acting act the
nanometer level we really should not expect results any different from
those obtained with ordinary macroscopic fillers.
Dispersion of Nanotubes
Poor compatibility between the CNT surface and the matrix lead to difficulty in
exfoliating and debundling CNTs. Poor adhesion of the matrix causes poor
dispersion, phase separation and aggregation of the CNTs making incorporation of
untreated CNTs into polymers difficult.
Several companies have now begun to address these issues by developing
proprietary compatibilizers:
Polymer compatible functionality
CNT Surface compatible functionality
Dispersion of Nanoclay
Clay Particle Clay Platelets
Clay particles consist of groups of stacked platelets. The challenge is to process the
clay nanocomposite so as to achieve complete dispersion of individual platelets.
Dispersion of Nanoclay
Nanoclay must be organically modified in order to achieve compatibility with a
polymer matrix. Long chain alkyl ammonium cations are typically used
N
HO
OH +
Source: Southern Clay Source: Southern Clay
Dispersion of Nanoclay
Source: Southern Clay
Source: Southern Clay
Source: Southern Clay
Good Dispersion,
considered complete
Partial Dispersion,
considered incomplete
Poor Dispersion
Dispersion with POSS

50 wt% loading
and transparent!
phase inversion
Blended into 2 million MW Polystyrene
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R R
R = cyclopentyl
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
R = cyclopentyl
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
R = styrenyl
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
R = Phenethyl
partial compatibility
domain formation
Dispersion with POSS

Imaging studies on Nanoreinforced

PP fibers
Molecular Silica dispersion confirmed at molecular level.
* Each black dot represents a 1.5 nm POSS

cage.
Source: Viers - US Air Force Research Laboratory
*scale =50nm.
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
R
Si
O
Si
O
Si
O
Si
O Si
O
Si
O
Si
O
Si
O
Si
O Si
O
Si O
O
Si
R
R
R
O
O
R
R
O
O
O
R
R
R
R
R
R
R
Representative Suppliers of Nanoparticles
Raw materials SWCNTs-HiPco and CNI X Grades Carbon Nanotechnologies, Inc
Raw Material Metal oxides-NanoArc, NanoDur, NanoGard Nanophase
Concentrates CNTs-Kentera Zyvex
Concentrates CNT-Nanoin Nanoledge
Raw Material, Masterbatch CNTs Nanocyl
Raw Material, Masterbatch MWCNTs-Graphistrength Arkema
Raw Material MWCNTs-Baytubes Bayer MaterialScience
Masterbatch MWCNTs-Fibril Hyperion
Compounded products Nanoclay-nanoSEAL Nycoa
Compounded, Concentrates Nanoclay-Nanoblend Polyone
Compounded products Nanoclay, Nanotube RTP Company
Compounded polyolefin Nanoclay-Hyfax Basell
Compounded nylon Nanoclay-Nanomed Foster Corp.
Raw Material Nanoclay-Closite Sothern Clay
Raw Material & Masterbatch Nanoclay-Nanomer, Imperm Nanocor
Raw Material & Masterbatch POSS Hybrid Plastics
How supplied Material supplied Company
Representative Applications of Nanotubes
For the most part, the plastics industry has focused on the use of MWCNTs,
primarily because they are lower cost and the difference in property enhancements
relative to SWCNTs is slight.
Largest use of CNTs is for electrostatic dissipation. Also targeted are improved
mechanical and thermal properties.
In the area of electrostatic dissipation the two largest applications are in automotive
and electronics handling equipment.
In automotive applications CNTs are used in body parts to provide a Class A
surface for electrostatic painting. Another automotive application is fuel line
components such as pumps, lines and housings.
In electronics applications CNTs are used in trays for wafer manufacturing and in
housings for disk drives.
Many applications are in sporting goods to improve mechanical properties of
composites.
Competes with carbon black and carbon fiber.
Representative Applications of Nanoclay
Applications in plastics principally revolve around improving barrier
properties, flame resistance, thermal and structural properties.
Early commercial targets were in automotive and packaging applications.
For automotive applications the target has mainly been weight savings, as
lower loadings of nanoclay can be used to reinforce polymers vs. other
mineral fillers. Clay nanocomposites also provide better surfaces, reduced
CTE and are potentially amenable to recycling.
In packaging the target has been barrier properties. Mainly in the area of
beverages. Other barrier applications have focused on tires and sporting
goods (balls).
Applications for improving fire resistance of plastics also vigorously
pursued.
Competes with traditional inorganic fillers.
Representative Applications of
Metal & Metal Oxides
Primary applications in plastics include antimicrobial, fungal and mold
resistant materials.
Other applications include protection from visible and UV light and
abrasion resistant coatings.
Representative Applications of POSS

Major focus on aerospace and defense applications.
Radiation hardening and shielding.
Food Packaging.
Electronic materials.
Space Resistant materials.
POSS

Barrier in Food Packaging

!POSS

incorporation provides longer product shelf life.

!Improves color printing.
POSS

Oxidation Resistance
MISSE 1 POSS Polyimide Samples: Erosion Depth (m)
POSS

Oxidation Resistance
LER 6.0 nm
Etch Capabilities in Bilayer Resist Design
SLR Resist
Si-based Resist
B
e
f
o
r
e

S
t
r
i
p
A
f
t
e
r

S
t
r
i
p
LER 5.0 nm
LER 6.6 nm
LER 12.9 nm
Much Improved LER after Pattern Transfer due to
Excellent Etch Characteristics of Silicon-based Resist
POSS

Oxidation Resistance
No Pattern Collapse after Etch Transfer
(75 nm line/150nm Pitch)
S i l i c o n b a s e d r e s i s t c a n s u p p o r t
high aspect ratio due to excellent etch selectivity
75nm L/S after dry
development of UL
POSS

Tooth Restoration Products

Examples of Commercial Nanocomposites
Source: Southern Clay
Source: GM

While reports on the use of nanocomposites in
automotive applications were quite frequent as
recently as 2005, there has been a significant
reduction since. Some sources reported that
Nanocomposites would be used in 2006 models,
but it is unclear how much is currently being
used.
Examples of Successful Nanocomposites
Source: Oceanit
Nanotube-containing surfboard
is tested near San Francisco.
Source: Montreal Hockey
Source: Nanoledge

Additional examples include
golf clubs, tennis rackets,
sail boat masts, and skis.
Triton Systems, Inc. - Converse All Star He:01 using ORMLAS polymer
nanocomposite discontinued after initial launch.
InMat, Inc. - Wilson discontinues development of Double Core tennis
ball after initial launch.

Commercial Success can be Short Lived
Honeywell Aegis NC - no longer manufactured. Aegis OX no longer
contains nanocompoite.
Eastman Chemicals Nanocomposites - after significant effort in the area,
intellectual property portfolio for polymer nanocomposites was donated to
the University of South Carolina.
Truths about Nanotechnology
For a successful technology, reality must take precedence
over public relations, for Nature cannot be fooled.
Richard Feynman
US educator & physicist (1918 - 1988)
Truths about Nanomaterials
Nano is not as important as the solution it provides.
Nano has no intrinsic merit other than what it does!
The entry and market capture for nanosolutions
requires vastly more time, capital, and support
than anyone is willing to admit.
Each nanosolution must earn a right to survive
via the application of hard science and economics
rather than reliance on slick marketing.
Trouble Brewing?
Earlier this year DuPont and Environmental Defense combined to launch
a Nano Risk Framework. The framework is designed to provide a
systematic and disciplined process to evaluate and address the potential
risks of nano-scale materials.
In 2005 the EPA announced that it was reclassifying nanosilver as a
pesticide.
In 2005 the Berkeley, CA City Council approved an amendment to their
hazardous materials law to include nano-sized particles which requires
researchers and manufacturers to report what materials they are working
with and how they are handling them. Earlier this year the Cambridge,
MA City Council announced that it is considering a similar law.
Several studies have indicated that carbon nanoparticles might act as
cytotoxins while others have shown that CNTs can have an asbestos like
effect on lung cells. Other studies have found no links between carbon
nanoparticles and cytotoxic effects.
Thank You
Si
Si
O
O
Si
Si
Si
Si
O
O
O
O
Si
O
Si
O
O
O
O
O
R
R
R
R
R
R
R
R