DuPont Nanoscale Science & Engineering: Reality & Promise

Homi C. BhedwarDirector,

DuPont Knowledge Center, Hyderabad

EmTech India 20109 March 2010

Bangalore

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New Technologies Generate …Hope, Fear,

Prentice Hall PTR; 1st edition (November 8, 2002)

Harper Collins; 1st edition (November 1, 2002)

Prometheus Books (December 30, 2005)

and Skepticism

3

1802 1830 1850 1900 1925 1945 1990 2000 2050 2090

Birth

Growth

Maturity

Birth

Growth

Maturity

Birth

Growth

Explosives

Chemistry,Polymers

Integrated Science:Biology, Chemistry, Materials Science,Knowledge Intensity

Maturity

DuPont: 207 Years of Product InnovationTo be the world’s most dynamic science company, creating

sustainable solutions essential to a better, safer, healthier life for people everywhere.

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DuPont Known & Admired for Innovation

5

Integrated Science

N

Chemistry

Nanoscience & Engineering

Materials Science

Biology

CompetitiveAdvantage

6

DuPont R&D Building Blocks….

ChemicalSynthesis (organic,

inorganic, fluoro)

Polymersynthesis & processing

Advanced Fibers

Particle &Dispersion

Science

Biology and bio-based processes

Materials Science Catalysis

Precision Patterning

Surfaces and

coatings

Inorganic- Organic

composites

Leverageable Analytical Science, Toxicology, Scientific Computing

Nanoscale Science and Engineering

….are all connected to NS&E

Leverageable Analytical Science, Toxicology, Scientific Computing:The Key to Nano-Progress“New truths become evident when new tools become available.” - Rosalyn Yalow (Nobel Laureate, ‘77)

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All That is “Nano” is Not New

David, stained-glass window, 19th century, Winchester Cathedral, England

http://student.britannica.com/eb/art-16461/David-stained-glass-window-19th-century-Winchester-Cathedral-England

A Damascus sword – 17th century Blade showing the damask microstructure

and remnant of cementite nanowires enclosed in CNT

http://news.softpedia.com/news/Damascus-Swords-Product-of-Nanotechnology-40503.shtml

http://www.ias.ac.in/currsci/feb2007/279.pdf

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“Established” nanosized materials:

- Carbon Black

- Colloidal silver and gold

- Colloidal and fumed silica

- Pigments

- Magnetic materials

- Catalysts

Sauer, McLean

Wood, Chou

Anhydride Surlyn®

modifier in Nylon-6

500 nm85 nm

AFM image showing distribution of hard (bright) & soft segments in elastane fiber

Web structure in PTFE membrane

Coatings on pigmentary TiO2

All That is “Nano” is Not New to DuPont

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Particle science

Inorganic and organometallic chem.Photochemistry Surface SciencePolymer ScienceDispersionsCoatingsColor SciencePrecision PatterningOrganic SynthesisFluorochemistryBiomolecular Eng.Materials Sci & Eng.Process innovations

Technology Toolkit

Construction

Security and Protection

Agriculture

Displays

Alternate Energy

Electronics

Automotive

Elect. machinery

Plastics

Markets Served

Surface properties

Optical properties

Elect. properties

Selective barriers

Heat resistance

Weight vs. strength

Flexibility

Biological activity

UV resistance

Cost vs.performance

Properties Needed

Displays

Advanced CoatingsFuel CellsPhotovoltaic CellsPrecision patterningProtective Apparel

Advanced Membranes

Engineering PlasticsElectronic MaterialsBiosensors

Target Applications

Market-Focused Innovation Strategy

Nanoparticles and dispersions

MetalsMetal oxidesNanoclays

Carbon nanotubesBiomoleculesMembranesALD / Thin Films- etc- etc

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Nanoscience Enables Unique Properties & Combinations

Rheological

Opt

ical

Electrical

Therm

alSur

face

Barrier

Electronic

Mechanical

Unique Unique Combinations?Combinations?

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Nanostructure-based Behavior of Materials is Determined by:

Relationship to other critical dimensions… • Size or structure relative to wavelength of visible light (400nm -700nm)

• Size or structure relative to molecular building blocks of bulk materials

• Size or structure relative to biological building blocks

• Active surface area relative to gross volume

• Effective surface area relative to nominal dimensions

And fundamental, size related properties• Quantum effects (e.g., quantum dots, single electron devices)

• Molecular architecture creating new forms of matter (buckyballs, carbon nanotubes)

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Surfaces(Patterned or textured on the nanoscale)

Levels of Nanoscale

Design

Films and coatings(Nanoscale in surface thickness only)

Nano Particles(nanoscale in one or

more dimensions)

50 nm50 nm

Nanodevices

Partitioning the Innovation Space for Materials…..Nanostructured bulk materials(nanoscale internal structure)

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DuPont (TM) Light Stabilizer 210 offers protection from the sun's UV rays for plastics used in products such as playground equipment, outdoor furniture and construction components.

Introducing: DuPont (TM) Light Stabilizer 210 Helps Protect Plastics from Sun Damage

First Product Developed Using DuPont-Environmental Defense Nano Risk Framework

WILMINGTON, Del., Oct. 15, 2007 – DuPont today introduced DuPont(TM) Light Stabilizer 210, a product designed as sun protection for plastics. The product uses extremely small particles of titanium dioxide to efficiently absorb ultraviolet light, protecting plastic and anything it covers from the sun’s damaging rays. Because a sizeable percentage of titanium dioxide particles in the product are nanoscale, it was selected as a demonstration case for application of the Nano Risk Framework that DuPont and Environmental Defense introduced in June. The Framework is a systematic and disciplined process to evaluate and address the potential risks of nanoscale materials.

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Attenuation of UV Radiation by DuPont™ Light Stabilizer 210

Polymer

DuPont™ Light Stabilizer 210 Particles

Io

Ir

Is

It

Ia

• Attenuation defined as the total UV screening effect, due to both UV absorbance and scattering.

• Optimized particle size to provide broad spectrum UV attenuation.

• Longer effective path length

Anderson, M. W., J .P. Hewitt, S. R. Spruce, Broad-Spectrum Physical Sunscreens: Titanium Dioxide and Zinc Oxide in Sunscreens, N.J. Lowe., Ed., Marcel Deker, Inc., New York, 1997, p 365

Io = incident radiation

Ir = reflected

Ia = absorbed

Is = scattered

It = transmitted

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TiO2 Nanoparticles Provide UV Stabilization

Hytrel® property retention after UV exposure

Particles Size Distribution of Ultrafine TiO2 Products

0.00

5.00

10.00

15.00

20.00

25.00

10 100 1000 10000

Particle Size (nm)

We

igh

t F

rac

tio

n (

%)

DLS 210

UF TiO2 #1

UF TiO2 #2

UF TiO2 #3

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Levels of Nanoscale

Design

Films and coatings(Nanoscale in surface thickness only)

Nano Particles(nanoscale in one or

more dimensions)

50 nm50 nm

Nanodevices

Partitioning the Innovation Space for Materials…..Nanostructured bulk materials(nanoscale internal structure)

Surfaces(Patterned or textured on the nanoscale)

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DuPont SuperStructural Overview T

ensi

le S

tren

gth

Tensile Modulus

Steel

AlFuture

Mg

EP

Structural Engineering

Polymers

0 200 GPa

0

500MPa

Hybrid solutions to close gap on metals• METAFUSE™ NanoMetal/Polymer hybrid• other…

New Product and Solutions Development to Replace Metals

20GPa

Improved resinsfor plastic structures• Long fibre reinforced (LFRT)• Stiffer via carbon fibre

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Nanocrystalline Metal Alloy Cladding

Polymer Substrateeg. compound, composite, film etc.

Nanometal/Polymer Hybrid Solution

Concept:Apply thin layer of nanocrystalline metal onto selected areas of a molded plastic part to increase stiffness and other properties.

Unique:NanoMetal clad on plastic dramatically improves part stiffness because nanometal is ultra strong, can withstand high tensile loads at part surface when flexed

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Scanning Electron Micrographs (SEMs) Illustrating the Crystalline Structure

Conventional metal Nanocrystalline metal

15 µm 15 µm

NanoCrystalline Metals

• Based on patented technology/proprietary process

• Produces fully-dense metals/alloys

• Extreme grain refinement results in high strength and hardness/wear-resistance

15µm

1nm

15µm

y = 0 +K

d

20

25% GR PA66

0

10

30

GP

a

Flexural Modulus

Plast

ic on

lyPla

stic/

Met

al

20

0

10

20

To

tal E

ner

gy,

Jo

ule

s

Plast

ic on

lyPla

stic/

Met

al

Multi-axial Impact

100 µm NanoMetal alloy clad on 25% GR PA66

DMA Curves

Plastic only

Plastic/Metal

METAFUSE™ NanoMetal/Polymer HybridMuch Higher Performance than Polymer Alone

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METAFUSE™:NanoMetal/Polymer Hybrid Solution

Nanocrystalline metal clad on polymer offers high performance with new design freedom:

Designing for high strength and stiffness at minimum weight Direct fabrication of structural components in complex shapes Improving strength, stiffness and creep of plastic parts at elevated

temperatures Adding hard, wear resistant coating to plastics Make plastics more impermeable, conductive and dimensionally stable Aesthetics / metal look

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2000 2005 2010 2015 2020 2025

Co

mp

lexi

ty

Surface/Interface Control

Nanostructured Polymers

3-D Nanofabrication

Selectively Permeable Membranes

Biointeractive

Lightweight Structures

Smart/Interactive Textiles

Nanoscale Building Blocks – variety of shape, size, composition

Specialty

Coatings

Hierarchically-Structured Materials

Multifunction composites

Directed, Self Assembled MaterialsFuel Cell/Solar Cell

DEVICE/APPLICATION

SCIENCE

Slide Provided by Jim Murday, NRL

Mechanical properties at nanoscale

Integrated model nano-macro

“Aldrich” catalog of nanostructures

Cost effective 3-D nanoassembly

Plethora of systems with “Nano inside”

Nanostructure in metals

High Power Ceramic Laser

http://www.chemicalvision2020.org/nanomaterialsroadmap.html

A Nanomaterials “Roadmap”

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NS&E is relevant to virtually every materials market…

1-4

5-8

9-14

15+

Medical applications

Bio-materialsTissue/

organ regen

NanobioNEMS

Smart implants

Drugdelivery

Medicaldiagnostics

Nano-arrays

Years

Coatings & Dispersions

Chemical catalysts

Textiles

Lubricants

CoatingsCosmetics

Paints

Devices & Microelectronics

Micro-processors

Quantum computingSimple

ICs

Memory/

Storage devices

Sensors

Displays

Molecularcircuitry

Energy, Industrial

Composites

Membranes

Food packaging

Energy/

fuel cellsSolar cells Prototype FED with carbon nanotubes

DNA wrapped around an individual

carbon nanotube

Low-cost

Energy

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DuPont is Leading in Nanomaterials Stewardship

Strategic Collaborations• Worked with Environmental Defense to publish a practical framework to identify,

manage and reduce SHE risks

• Leading 14 company consortium to develop new tools and techniques for generating nanoparticle safety data and monitoring safety

Establishment of Standards• Engagement with external industry peers, academia, NGOs and standards development

organizations

• Engagement with EPA and OECD

Conducting and publishing toxicology studies • DuPont Haskell Lab. widely recognized as a leader

Active internal coordination & alignment • “One DuPont” guidelines established for nanomaterials development and

commercialization

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Nanoparticle Occupational Safety and Health (NOSH) Consortium

A consortium of companies, government, academia, and public interest groups, including*:

DuPont Procter & Gamble Dow Chemical Air Products & Chemicals

DeGussa Rohm & Haas PPG Health & Safety Executive (UK)

Intel Corporation Dept of Energy Office of Science General Electric

Sponsored research at DuPont to advance our ability to assess and control occupational exposures to engineered nanoparticles

• Generate nanoparticle aerosols and measure their behavior as a function of time

• Develop a simple, robust, portable device to measure airborne nanoparticles

• Measure the barrier efficiency of various materials to nanoparticles

Cost shared among 14 organizations

* Other organizations have requested that their identities not be disclosed

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Environmental Defense – DuPont Draft Nano Risk Framework

“A framework to facilitate the responsible development, production, use and disposal of nano-scale materials.”

• Collaboration begun in October 2005

• Objective: A systematic and disciplined process, developed with broad collaboration

• to identify, manage and reduce potential health, safety and environmental risks throughout the lifecycle of such nanomaterials”

• Model and tool for industry, public interest groups, academia and government

• Make available information, tools and methods developed

• Framework was published on June 21, 2007

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Summary

• Strong tradition of R&D and innovation.

• Nanotechnology is yet another tool in DuPont’s technology tool-kit.

• Nanotechnology can deliver value through ordered hierarchies.

• DuPont is a leader in Nanomaterials stewardship