Practical Use of

Nanomaterials in Plastics
Innovative Technologies
Symposium for Plastics
July 31, 2007

Joseph J. Schwab

Hybrid

Plastics

www.hybridplastics.com

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
Nanostructured
Materials
Nanoparticles
Nanocomposites
Supramolecular
Assemblies

Nanotools

Nanodevices

Fabrication
Techniques

Molecular
Electronics

Instrumentation
Metrology &
Analysis

Mems &
BioMems

Software
Computation
Simulation

Lab on Chip
Sensors &
Detectors
Device
Miniaturization

Representative Types of Nanoparticles

Nanoparticles
Carbon Tubes
-Single Walled
-Multi Walled

Fullerenes

POSS
-Molecular Silicas
-Monomers
-Silanols
-Polymers

Dendrimers
Graphenes
Clays
-Montmorillonite
-Halloysite
-Vermiculite

Nanofibers
Metal & Metal Oxides
Silica

Why is Nano Important in Materials?

Field
1 mm
Sewing Needle
Razor Blade Thickness

100 m

10 m
1 m

Tunneling

1-100 nm

Optical

Quantum Well

1-100 nm

Wave Decay

10-1000 nm

Primary Structure

0.1-10 nm

Secondary Structure

10-1000 nm

Dislocation Interaction

1-1000 nm

Crack Tip Radius

1-100 nm

Entanglement Rad.

10-50 nm

Human Hair

Mechanics

Bacteria, Fillers &

Polymer Morphology

Therm-Mech. Chain Motion

0.5-50 nm

Viruses & Nanofillers

Nucleation

Defect

0.1-10 nm

Critical Nucleus Size

1-10 nm

Surface Corrugation

1-10 nm

Catalysis

Surface Topology

1-10 nm

Biology

Cell Walls

1-100 nm

Membranes

Porosity Control

0.1-5 nm

100 nm
10 nm
1.0 nm
0.1 nm

Critical Length

Electronics

Polymers

Most Cells & Fibers

Property

POSS Building Blocks

Macromolecules
Atoms / Small Molecules

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:Peter Harris

Source:Wikimedia Commons

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

C60Fullerene

OR

Endohedral
C60Fullerene

Chemically Modified C60Fullerene

Timeline for Fullerenes

(A Cautionary Tale)

In 1985 C60 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 Japanese companies have purchased samples. Claims that commercial
products in Japan 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:Southern Clay

Source:Wikimedia Commons

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

Metal oxide nanoparticles are actually isolated as

agglomerates, typically over 1,000 nanometers in
size, and behave similarly to conventional powders.
Source:Nanophase Technologies

POSS Nanostructures
Unreactive organic (R)
groups for solubilization
and compatibilization.

Si

Si
O

Si

R
O

Si

Nanoscopic size
Si-Si distance = 0.5 nm
R-R distance = 1.5 nm.

One or more reactive

groups for grafting or
polymerization.

R O

O
Si

Si

Si

R
Si

O
R

Thermally and chemically

robust hybrid
(organic-inorganic)
framework.

Precise three-dimensional structure for

molecular level reinforcement of polymer
segments and coils.
R
O

Si
O

Si
O

Si

O
Si

Si

O
Si

R
Si

O
R

Metal Containing

Si
R

Si
O

OH
Si

O
R

Si

OH

OH

O
Si

Si

R
Si

O
R

Stable Silanols

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 m2/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

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.

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

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:

CNT Surface compatible functionality

Polymer 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
+

OH

HO

Source: Southern Clay

Source: Southern Clay

Dispersion of Nanoclay

Source: Southern Clay

Poor Dispersion

Source: Southern Clay

Partial Dispersion,
considered incomplete

Good Dispersion,
considered complete

Source: Southern Clay

Dispersion with POSS

Blended into 2 million MW Polystyrene
R

Si
O O

Si

O
Si

Si

R = cyclopentyl

Si O

R
Si
O
Si

Si

Si O

R O
O
Si
O

Si
R

R = styrenyl

Si
O

Si

R
Si
O

Si
O O

O
O

Si

R
Si

Si

Si
O

partial compatibility

Si
O O

R = cyclopentyl

domain formation
R

R O

Si

R
Si
O

Si

Si O

Si

O
Si
O

R O
O

R
Si
O

Si

Si

Si

R O
O

O
Si

Si
O
R

R = Phenethyl

phase inversion

50 wt% loading
and transparent!

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.
R
R

Si

Si

Si

O
R

R
Si

O
O

O
Si

Si

Si

Si

R
O

O
R O
O

O
R

Source: Viers - US Air Force Research Laboratory

Si

O
Si

*scale = 50nm.

R O
O

R
Si
O

Si
O
Si
R

Si

Si
O O

Si

Si
Si

O Si
R

O O

Si O
R

Representative Suppliers of Nanoparticles

Company

Material supplied

How supplied

Hybrid Plastics

POSS

Raw Material & Masterbatch

Nanocor

Nanoclay-Nanomer, Imperm

Raw Material & Masterbatch

Sothern Clay

Nanoclay-Closite

Raw Material

Foster Corp.

Nanoclay-Nanomed

Compounded nylon

Basell

Nanoclay-Hyfax

Compounded polyolefin

RTP Company

Nanoclay, Nanotube

Compounded products

Polyone

Nanoclay-Nanoblend

Compounded, Concentrates

Nycoa

Nanoclay-nanoSEAL

Compounded products

Hyperion

MWCNTs-Fibril

Masterbatch

Bayer MaterialScience

MWCNTs-Baytubes

Raw Material

Arkema

MWCNTs-Graphistrength

Raw Material, Masterbatch

Carbon Nanotechnologies, Inc

SWCNTs-HiPco and CNI X Grades

Raw materials

Nanocyl

CNTs

Raw Material, Masterbatch

Nanoledge

CNT-Nanoin

Concentrates

Zyvex

CNTs-Kentera

Concentrates

Nanophase

Metal oxides-NanoArc, NanoDur, NanoGard

Raw Material

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

Etch Capabilities in Bilayer Resist Design
SLR Resist

After Strip Before Strip

LER 5.0 nm

LER 12.9 nm

Si-based Resist

LER 6.6 nm

LER 6.0 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)

75nm L/S after dry

development of UL

Silicon based resist can support

high aspect ratio due to excellent etch selectivity

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

Nanotube-containing surfboard
is tested near San Francisco.

Source: Oceanit

Source: Nanoledge

Source: Montreal Hockey

Additional examples include

golf clubs, tennis rackets,
sail boat masts, and skis.

Commercial Success can be Short Lived

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.

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
R
R

O
Si

Si
O

Si
Si

R
Si
O
Si

O
RO

O
Si

Si O
R