November 2002 1

Defense University Researchon

Nanotechnology

Dr. Clifford LauOffice of Basic Research, DUSD

703-696-0431Clifford.lau@osd.mil or lauc@onr.navy.mil

November 2002 2

Historical Perspective

DoD recognized the importance of nanotechnologyin the early 1980s when research sponsored by DoDbegan to approach nanometer scale, although wedidn’t call it nanotechnology at the time.

1980 1990 2000

MicroelectronicsPhysicsChemistryMaterialsMolecular biology

Nanotechnology

(NNI)

November 2002 3

* NANOELECTRONICS/NANOPHOTONICS/NANOMAGNETICSNetwork Centric WarfareInformation DominanceUninhabited Combat VehiclesAutomation/Robotics for Reduced ManningEffective training through virtual realityDigital signal processing and LPI communications

* NANOMATERIALS “BY DESIGN”High Performance, Affordable MaterialsMultifunction, Adaptive (Smart) MaterialsNanoengineered Functional MaterialsReduced Maintenance costs

* BIONANOTECHNOLOGY - WARFIGHTER PROTECTIONChemical/Biological Agent detection/destructionHuman Performance/Health Monitor/Prophylaxis

DoD Focused Areas in NNI

November 2002 4

Enhanced warfighting capabilities

* Chem-bio warfare defenseSensors with improved detection sensitivity and selectivity, decontamination

* Protective armors for the warriorStrong, light-weight bullet-stopping armors

* Reduction in weight of warfighting equipmentMiniaturization of sensors, computers, comm devices, and power supplies

* High performance platforms and weaponsGreater stealth, higher strength light-weight materials and structures

* High performance information technologyNanoelectronics for computers, memory, and information systems

* Energy and energetic materialsEnergetic nano-particles for fast release explosives and slow release propellants

* Uninhabited vehicles, miniature satellitesMiniaturization to reduce payload, increased endurance and range

November 2002 5

DoD Investment on Nanotechnology

FY2000 FY2001 FY2002 FY2003

DoD $70M $123M $180M $201M

OSD $ 28MDARPA $101MArmy $ 23MNavy $ 31MAir Force $ 18M

November 2002 6

DoD Programs in Nanotechnology

• OSDMultidisciplinary University Research Initiative (MURI), DEPSCoR, NDSEG

• DARPABio-molecular microsystems, metamaterials, molecular electronics, spin electronics, quantuminformation sciences, nanoscale mechanical arrays

• ArmyNanostructured polymers, quantum dots for IR sensing, nanoengineered clusters, nano-composites,Institute for Soldier Nanotechnology (ISN)

• NavyNanoelectronics, nanowires and carbon nanotubes, nanostructured materials, ultrafine and thermalbarrier nanocoatings, nanobio-materials and processes, nanomagnetics and non-volatile memories,IR transparent nanomaterials

• Air ForceNanostructure devices, nanomaterials by design, nano-bio interfaces, polymer nanocomposites,hybrid inorganic/organic nanomaterials, nanosensors for aerospace applications, nano-energeticparticles for explosives and propulsion

• SBIRNanotechnologies, quantum devices, bio-chem decontaminations

November 2002 7

DoD’s participation in the NNI

•In FY2001, as a part of the NNI, DUSD supportednanotechnology as follows

-Graduate Fellowship under NDSEG ($5M)-45 graduate students to major in nanotech-3-years at average of $45K/year-All over the country,e.g. MIT, GIT, UCB,

etc.

-Equipment for nanotechnology ($7.25M)-One year only

-DURINT research program ($8.75M)-$15M per year for 5 years

November 2002 8

Institution State Investigator Title of Equipment ProposalArizona State University AZ David K. Ferry Electron-Beam Lithographic Equipment

Harvard University MA George Whitesides Scanning Probe Microscope for Microstructure Analysis

Kansas State University KS HongXing JiangIII-Nitride Micro- and Nano-Structures and Devices - Growth, Fabrication, and Characterization

Lehigh University PA Martin P. HarmerA Focused-Ion Beam (FIB) Nano-Fabrication and Characterization Facility

Massachusetts Institute of Technology MA Subra Suresh

A Comprehensive Experimental Facility for Nano- and Meso-Scale Mechanical Behavior of Nano-Structured Materials and Coatings

Massachusetts Institute of Technology MA Terry Orlando

Very Low Temperature Measurement System for Quantum Computation with Superconductors

Pennsylvania State University PA A. Welford CastlemanPhotoelectron Spectrometer and Cluster Source for the Production and Analysis of Cluster Assembled Nanoscale Materials

Rice University TX Richard E. SmalleyMagnetic/RF Field Assisted Spinning of Carbon Single Walled Nanotube Fibers

Stevens Institute of Technology NJ Hong-Liang Cui

The Science and Technology of Computational Nano/Molecular Electronics - Equipment Proposal

University of California at Santa Barbara CA Horia Metiu

Catalysis by Nanostructure: Methane, Ethylene Oxide, and Propylene Oxide Synthesis on Ag, Cu, or Au Nanoclusters

Univ. of Illinois at Urbana Champaign IL Dana D. Dlott

Ultrafast Vibrational Spectrometer for Engineered Nanometric Energetic Materials

University of Arizona AZ Hyatt M. Gibbs Nanotechnology InstrumentationUniversity of Colorado CO Josef Michl Equipment for Molecular Rotors

University of Michigan MI Stella Pang Science and Technology of Nanostructures for Advanced Devices

University of Texas TX Brian A. KorgelAcquisition of an Electron Beam Lithography System for the Study of Nanstructures Formed using Bioinspired Self-Assembly Processes

University of Virginia VA James Fitz-GeraldAcquisition of a High-Resolution Field Emission Electron Microscope for Nanoscale Materials Research and Development

Western Kentucky University KY Wei-Ping Pan Acquisition of an x-Ray Diffractometer for Nanotechnology Research

FY01 DURINT Equipment Program

November 2002 9

FY01 DURINT Research Program

Investigator Prime Institution State DURINT Topic Agency

Josef Michl University of Colorado CO Nanoscale Machines and Motors Army

Mehmet Sarikaya University of Washington WAMolecular Control of Nanoelectronic and Nanomagnetic Structure Formation Army

Michael R. Zachariah University of Minnesota MN Nano-Energetic Systems Army

Hong-Liang Cui Stevens Institute of Technology NJCharacterization of Nanoscale Elements, Devices, and Systems Army

Richard Smalley Rice University TXSynthesis, Purification, and Functionalization of Carbon Nanotubes Navy

Stephen Chou Princeton University NJ Nanoscale Electronics and Architectures Navy

Randall M. Feenstra Carnegie Mellon University PANanoporous Semiconductors - Matrices, Substrated, and Templates Navy

Subra SureshMassachussetts Institute of Technology MA

Deformation, Fatigue, and Fracture of Interfacial Materials Navy

Horia MetiuUniversity of California at Santa Barbara CA Nanostructures for Catalysis Air Force

Mary C. BoyceMassachussetts Institute of Technology MA Polymeric Nanocomposites Air Force

Paras PrasadState University of New York at Buffalo NY Polymeric Nanophotonics and Nanoelectronics Air Force

Terry OrlandoMassachussetts Institute of Technology MA Quantum Computing with Quantum Devices Air Force

James LukensState University of New York at Stony Brook NY Quantum Computing with Quantum Devices Air Force

Chad A. Mirkin Northwestern University ILMolecular Recognition and Signal Transduction in Bio-Molecular Systems

DARPA/Air Force

Anupam MadhukarUniversity of Southern California CA

Synthesis and Modification of Nanostructure Surfaces

DARPA/Air Force

George Whitesides Harvard University MAMagnetic Nanoparticles for Application in Biotechnology DARPA/Navy

November 2002 10

The New Stochastic (Digital) SensorNon-Ensemble-Averaged Information at the

NanoscaleProf. Hagen Bayley, Texas A&M University

Hagan Bayley (TAMU)

Infinitely engineerable (e.g. M++ Site)

The Nanomachine: -Hemolysin Channel

Transiently bound analyte

blocks ion flow

Analytes + ion flow

Lipid bilayer

The Principle: Single Channel Ion Conductance Genetically Engineered M++ site

analyte-bound site

av av

Open site

pAmsec

Analyte Concentration Analyte Signature

Issues Under Investigation Display options (supported

bilayers, nanotubular membranes) Interrogation (microwave, optical) Multi-valent oligosaccharide

receptors Commercialization Fluidics (M/NEMS)

Performance digital, information-rich output real chemical time, reagentless, self-calibrating large dynamic range, no signal loss large analyte universe

M,++ organics, proteins, DNA, (viruses)

Cd Zn Co Cd Zn CoCd

Ternary M++ Mixture

November 2002 11

Cluster Engineered MaterialsProf. G.C. Schatz, Northwestern University

MURI, year started: 1997 Web URL: www.chem.nwu.edu/~muri

OBJECTIVES• Develop new approaches for making nanoparticles• Develop DoD applications for nanoclusters

RELEVANCE• DNA sensing• Protein detection• Infrared, visible and Raman spectroscopy• Optical materials, Eye/sensor detection

Nanoparticle-based DNA Sensors

Anthrax Detection

ACCOMPLISHMENTSDNA/Protein detection• Detection of one femtomole of anthrax with single base mismatch selectivity.• Zeptomole/nanoparticle sensitivity to streptavidin using a sensor with <100 nm dimensions.• Technology transfer to industry and Army

Optical materials• Designer nanoparticles for infrared and visible detection, nanooptics, eye/sensor protection•Technology transfer to ARL and NRL

A-T-T-A-C-C-G-C-T -X

A-A-C-T-T-G-C-G-C-T-A-A-T-G-G-C-G-A

Biological DNA

Biological DNA

A-A-C-T-T-G-C-G-C-T-A-A-T-G-G-C-G-AA-T-T-A-C-C-G-C-T -XX-T-T-G-A-A-C-G-C-G

X-T-T-G-A-A-C-G-C-G

Nanoparticle-based Protein Sensors

• Ultrasensitive• Specific• Label-Free• General• Small• Fast• Low-Cost• Simple

November 2002 12

GOAL – Develop a multilayer film structure to simultaneously sense and destroy chemical and biological warfare agents.

Schematic Multilayer Scavenger and Sensor Device

Prof. John Yates, University of Pittsburgh

MURI: Photocatalytically Active Nanoscale Scavengers and Sensors for CW and Biological Agents

CHALLENGES –1. Integration of both chemical and biological agent sensors and CB catalysts for their destruction into stable multifunctional films or coatings 2. Efficient photocatalysis in the visible spectrum3. Integration of the multifunction films into working devices.

DELIVERABLES –•Polymer-anchored enzyme and antibody scavengers and sensors for CB agents

•Visible-light activated doped-TiO2nanoparticles with non-photoreactive porous polymer support catalyzing the destruction of both chemical and biological agents

•Extremely active CaO and MgO and MgO-Cl2nanoparticle material for the degradation of CB agents, supported in polymer films.

PRIOR WORK –•University of Pittsburgh research on TiO2photocatalysts and polymer anchored enzymes and sensors.•Kansas State University work on active nanoparticle oxide adsorbents.•Texas A&M University work on antibody-based scavengers.

November 2002 13

REACTIVE METAL OXIDE NANOPARTICLES

FOR SOLDIER PROTECTION Research Objective: Synthesis, characterization, and application of reactive metal oxide nanoparticles for protection against chemical and biological warfare agents and ballistic protection

Transitions: ARO program supports Professor Ken Klabunde at Kansas State University collaborating with ECBC Next Generation Sorbent Decontamination Program(FY09), Domestic Preparedness Office at SBCCOM, Reactive Protective Skin Cream program at USAMRICD, PM for Nonstockpile Chemical Demilitarization, Ballistic protection programs at Natick Soldier Center. R&D Partners: ARL-ARO/ECBC/NSC/USAMRICD/Universities/Industry

Payoff: Highly effective enhanced reactivity for the degradation of chemical and biological agents with reduced materiel burden. Enhanced Ballistic Protection for the soldier.

New Solutions for Decontamination and Protection of the Soldier in a Chemical and Biological Warfare Environment

—Surface area MgO

Commercially Available 30m2

Reactive Nanoparticles 500m2

•High Surface Area with increased

reactivity

November 2002 14

Institute for Soldier NanotechnologiesProf. Edwin Thomas, MIT

Investment Areas• Nanofibres for Lighter Materials• Active/reactive Ballistic Protection (solve energy

dissipation problem)• Environmental Protection• Directed Energy Protection• Micro-Climate Conditioning• Signature Management• Chem/Bio Detection and Protection• Biomonitoring/Triage• Exoskeleton Components• Forward Counter Mine

University Affiliated Research Center• Investment in Soldier Protection• Industry partnership/participation• Accelerate transition of Research Products

Goals• Enhance Objective Force Warrior survivability• Leverage breakthroughs in nanoscience &

nanomanufacturing

Supramolecular Self-Assembly

Mesoscopic Integration

Molecular Scale Control

Nano-Scale Devices

November 2002 15

Melt Processed Polymer/Clay Nanocomposites for

Biodegradable and Recyclable Packaging

Environmental Quality (EQ)Program 6.1

Jo Ann Ratto – Project Officer

U.S. Army Natick Soldier Center

508-233-5315

Fax 508-233-5363

Email joann.ratto@natick.army.mil

November 2002 16

Melt Processable Polymer Clay Melt Processable Polymer Clay Nanocomposites (EQ Program)Nanocomposites (EQ Program)

Objective Develop environmentally friendly packaging from nanocomposites to improve the military packaging and reduce waste.

Justification Reduce solid waste requirement

Accomplishments Produced nanocomposites with improved

thermal properties with no loss in mechanical, biodegradable, and barrier properties.

Produced blown films of PCL/clay and EVOH/clay with improved properties.

Investigated screw configuration on the interaction of clay/polymer

Transition to SERDP 3 publications – 11 invited talks

Pure EVOH vs. EVOH Nanocomposite(100 rpm) Oxygen Transmission Rate

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Neat EVOH EVOH/Clay

Oxy

gen

Tra

nsm

issi

on

Rat

e (c

m3 /m

2 /mil/

day

)

EVOH 1

EVOH 2

Milestones and Funding

FY 01

FY 02

FY 03

FY 04

Blown film extrusion of PCL/clay, PP/clay, PET/clay and EVOH/clay

x

Optimize processing, fully characterize and compare to military specification

x

Target MRE, injection molding, biodegradation studies complete

x

Scale-up, prototypes, replacement items

x

Total ($K) 220 220 200 195

November 2002 17

To develop a high barrier, non-foil material for incorporation into existing and future combat ration packaging systems to enhance shelf life and survivability.

Material compounding will be conducted to determine feasibility of incorporating nano-sized fillers into commercially available materials.

Processing trials will be conducted to determine feasibility of utilizing existing processing methods. Processing parameters will be optimized to enhance orientation of nanocomposite fillers such that gas diffusion will be minimized. Films will be evaluated for physical and barrier properties.

The novel material technology will: Increase shelf life Enhance package survivability Ensure ration safety Enhance producibility

Nano-clays successfully incorporated into polymers Nanocomposite films successfully processed

Nanotechnology for Optimization of Nanotechnology for Optimization of Barrier PropertiesBarrier Properties

U.S. Army – Combat Feeding ProgramU.S. Army – Combat Feeding Program6.26.2

Nanotechnology for Optimization of Nanotechnology for Optimization of Barrier PropertiesBarrier Properties

U.S. Army – Combat Feeding ProgramU.S. Army – Combat Feeding Program6.26.2

Nanoclay Composite Barrier Film

zz

Mica Type Silicate 0.5-2 micron Long 1 nanometer Thick Swell Platelets Intercalate Polymer

Montmorillonite Clay

TECHNICAL APPROACH:

OBJECTIVE

BENEFIT

ACCOMPLISHMENTS

November 2002 18

REDUCTION OF SOLID WASTE ASSOCIATED WITH MILITARY RATIONS AND

PACKAGINGPROJECT NUMBER PP-1270

6.2 Funded FYO2-04Dr. Jo Ann Ratto

U.S. Army Natick Soldier Center

November 2002 1919

Technical Objective and Approach

Objective:

To produce/replace Army packaging items with nanocomposites.

Incorporate clay nanoparticles into biodegradable and recyclable thermoplastic polymers to decrease solid waste and to improve heat deflection temperatures, mechanical and barrier properties.

Approach:

Melt process polymer/clay nanocomposites by incorporating small amounts of organically modified montmorillonite clay (1 – 5% by weight) with biodegradable/recyclable polymers and characterize the thermal, mechanical and barrier properties.

November 2002 20

NanocompositesNanocomposites

OBJECTIVES

• Develop high barrier, non-foil material

• Eliminate pinholes, flex cracking problems

• Improve barrier properties

• Enhance package survivability

• Enhance shelf life

• Enhance producibility

November 2002 21

MRE Pouch Material

Polyolefin

Aluminum Foil

Polyamide

Polyester

Inner Layer

Outer Layer

November 2002 22

MRE Performance Requirements

• MRE pouch is currently made from a multilayered film consisting of polyolefin (PP), foil, polyamide (PA), and polyester (PET)

• Oxygen Transmission Rate – 0.06 cc/m2/24 hrs• Water Vapor Transmission Rate – 0.01 gr/m2/24 hrs• With stand pouch abuse 32-160C

• Our Approach – Use 1-2 recyclable and/or biodegradable polymers with nanoclays to at least meet the specifications

November 2002 23

• Enhanced Heat Distortion Temperature• Enhanced Barrier Properties• Enhanced Physical Properties• Low Processing Cost• Single-step Processing• Light-weight

Commodity Polymers + 2-8 wt.% of layered silicate reinforcements

NANOCOMPOSITES

NanocompositesNanocomposites

November 2002 24

TECHNICAL APPROACHTECHNICAL APPROACHDevelop Non-Retortable Mono-layer Develop Non-Retortable Mono-layer

Packaging Structures for MRE ComponentsPackaging Structures for MRE Components

Scale up from lab scale twin screw extruder to industrial scale equipment (co-extruder, twin screw extruder)

Characterize the structures

Down-select films

Fabricate prototype structure

Performance testing

Transition technology

November 2002 25

Twin screw extruder

Blown film dieNanocomposite Blown

Film

Develop Non-Retortable Mono-layer Develop Non-Retortable Mono-layer

Packaging Structures for MRE ComponentsPackaging Structures for MRE Components