November 2002 1
Defense University Researchon
Nanotechnology
Dr. Clifford LauOffice of Basic Research, DUSD
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 [email protected]
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