What’s After Nanotechnology? Developing the Army’s Future Materials

1. What’s After Nanotechnology?Developing the Army’s Future Materials Dr. David M. Stepp U.S. Army Research Office Materials Science Division david.m.stepp@us.army.mil (919) 549-4329, DSN 832-4329, FAX (919) 549-4399 http://www.aro.army.mil 2 March 2005

2. The Hope for Army Transformation:Revolutionary Materials Today Objective Force < 30 lb. effective load Fit the C-130 “Crucible” ~100 lb. load < 20 tons 70+ tons 0 mph > 40 mph Innovation -- Accelerating the Pace of Army Transformation

3. Outline • Basic Research Definition • U.S. Army Research Office Overview • Types of Basic Research Awards • Major Focus Areas • DoD Nanotechnology Definition • Nanotechnology and Lightweight Materials • What’s After Nanotechnology? • Optimized Materials Design • Bio-hybrids • Improved Technology Transfer

4. Basic Research Defined(DoD 7000.14-R) Basic research is systematic study directed toward greater knowledge or understanding of the fundamental aspects of phenomena and of observable facts without specific applications towards processes or products in mind. It includes all scientific study and experimentation directed toward increasing fundamental knowledge and understanding in those fields of the physical, engineering, environmental and life sciences related to long-term national security needs. It is farsighted high payoff research that provides the basis for technological progress. Basic research may lead to: (a) subsequent applied research and advanced technology developments in Defense-related technologies, and (b) new and improved military functional capabilities in areas such as…

5. Needs Driven Research Opportunity Driven Research Lightweight Armor Materials Ultra-lightweight Structures Lightweight Power Sources Combat ID/IFF Amorphous Metals Computational Materials Science Unique Characterization Tools Microstructure Quantification Foamed Materials Self-healing Materials Basic Research Refined

6. U.S. Army Research Office(Research Triangle Park, NC) Chief Scientist Henry Everitt Director Jim Chang Legal Counsel Mark Rutter Operations Faye Rodgers Physical Sciences Doug Kiserow (A) Engineering Sciences David Skatrud Mathematical & Info Sciences Mark Swinson Resource Management George Arthur Mathematics David Arney Mechanical Sciences David Mann Physics Peter Reynolds (A) Computing & Info Sciences Randy Zachery Chemical Sciences Robert Shaw Materials Science David Stepp Information Management Bessie Oakley Outreach Programs David Camps Life Sciences Mimi Strand Acquisition Center Larry Travis Electronics William Clark Small Business Programs Susan Nichols Environmental Sciences Kurt Preston International Programs Jim Harvey/Sean Yu ~ 100 employees at RTP 45 PhD Program Managers

7. ARO Basic Research Awards http://www.aro.army.mil ARO’s Broad Agency Announcement Single Investigator Program (~$100k / year for 3 years) Conference / Symposium / Workshop Grants (~$5k for 12 months) Short Term Innovative Research, STIR (up to $50k for 9 months) Young Investigator Program, YIP (~$50k / year for 3 years) HBCU/MI Program (~100k / year for 3 years) Multidisciplinary Research Program of the University Research Initiative, MURI (~$1M / year for 5 years) DoD Experimental Program to Stimulate Competitive Research, DEPSCoR (>$350k for 3 years) Defense University Research Instrumentation Program, DURIP (~$200k for 12 months) Small Business Innovative Research, SBIR ($70k for 6 months → $50k for 4 months → $730k for 24 months) Small Business Technology Transfer, STTR (with “research institute” partner) ($100k for 6 months → $750k for 24 months) Externally Funded Programs

8. ARO Materials ScienceResearch Focus Areas • Mechanical Behavior of Materials • High strain-rate phenomena • Characterization tools • Deformation mechanisms • Lightweight damage tolerance • Property-focused processing • Computational materials theory • Toughening mechanisms • Tailored functionality • Active transport membranes • Self-assembling ceramics • Synthesis and Processing • Materials Processing • Field activated/enhanced sintering • Powder consolidation • Metastable materials and structures • Structural amorphous metals • Glass formability and transition • Ultra-fine grained materials • Physical Behavior of Materials • Heteroepitaxy • Interface formation + diffusion • Strain mismatch • Engineering epitaxial layers • Defect engineering • Semiconductors • Ferroelectrics • Functional materials & integration • Electronics • Magnetics • Optics • Actuation • Materials Design • Growth and processing design • Surface + interface engineering • Integrating dissimilar materials • Non-equilibrium processing • Modeling and simulation • In-situ & nanoscale characterization • High resolution spectroscopy • Nondestructive characterization • Process control for optimization

9. DoD Nanotechnology Defined DoD nanotechnology programs are distinguished from those of other federal agencies in that the program activities are simultaneously focused on scientific and technical merit and on potential relevance to DoD. The overall technical objective of these programs is to develop understanding and control of matter at dimensions of approximately 1 to 100 nanometers, where the physical, chemical, and biological properties may differ in fundamental and valuable ways from those of individual atoms, molecules, or bulk matter. The overall objective for DoD relevance is to discover and exploit unique phenomena at these dimensions to enable novel applications enhancing war fighter and battle systems capabilities.

10. Nanotechnology andLightweight Materials http://www.physics.umd.edu/robot/feynm/fphoto.html Courtesy AIP Niels Bohr Library Richard P. Feynman (1918-88)

11. http://www.greggman.com/japan/miraikan/miraikan.htm Motivating Nanotechnology(Richard P. Feynman, 1959) • Is it possible to write (legibly) the entire 32 volumes of the Encyclopedia Britannica on the head of a pin? • 600 pages each → 1.8M square inches Circle 125 ft across → 25,000x pin head • Resolving power of eye ≈ 1/120th inch Demagnifying by 25,000x → 8nm 8nm dot contains ≈ 1000 atoms “There’s plenty of room at the bottom” How would you write it? How would you read it? How would you copy it? • How can this impact lightweight materials for defense? } Dramatically increased feature density

12. Nanotechnology andLightweight Materials? Strengths • Unprecedented functional materials and functional structures • Feature densities (and surface areas) • Weight savings from reduced size of components • “Inserting” function into proven structural materials • Degradation resistance, surface-area-based enhancements • Features can be engineered below critical defect size • Multifunctional materials • Some enhancement from atomic-scale optimization, simulation • Most likely for highest-end applications (incremental)

13. 8 6 4 2 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Exploiting Nanoscale Structure(C. Schuh, MIT) Grain Size (nm) 100 25 11 6 4 3 2 Hall-Petch law Hardness (GPa) Nickel, literature data Ni-W alloys, current study -1/2 -1/2 (Grain Size) (nm) • Controlled electrodeposition for high quality metals (70 – 0 nm grain sizes) • Molecular statics simulations to enhance understanding of deformation • Unexpected behavior discovered – “nc” metals stronger in compression

14. "This isn't right. This isn't even wrong." http://www.geocities.com/ilian73/pauli.html Wolfgang Pauli (1900-1958)

15. Nanotechnology andLightweight Materials? Weaknesses • Excessive funding • Prolific “forced” nanotechnology focus in research proposals • Over-hyped and misleading results (esp. athletic equipment) • Relative improvements to substandard materials • Non-falsifiable hypotheses • Mechanical properties and extrapolating to design values • Micro/nano -scale testing does not correlate with bulk • Reliability and repeatability problematic • Material scale-up highly problematic • Processing control, variations, and durability • Nanotubes

16. Example: Actual Military Requests • “Injectable” training • Localized fluency in all languages; seamlessly blend into any cultural environment • Example: “Tactical neural nano-implant” • Integrated self-protection capabilities • Indestructibility; appear to be standard regional dress • Example: “Carbon nanotube armor” • Sensors and communications • Extend all senses; be able to detect stress or unusual behavior • Example: “Sensory enhancing nanobots” • Shape shift materials • Ability to blend with any environment • Example: “Nano-fabrics that self heal, self clean, and adopt color and texture of surroundings”

17. 600 Amorphous Alloys 500 400 Strength-to-weight Ratio 300 Window Glass 200 Aluminum Titanium Copper Steel 100 0 0 2 4 6 8 10 12 Density Optimized Material DesignIntegrating Experimental and Computational Materials Science V=998.7 m/s L0 = 4.51 cm Computational theory identified precise transport pathways in bacterial channels for the development of revolutionary protective membranes [T.L. Beck] Computational materials discovery enhanced development of leap-ahead anti-armor materials [W.L. Johnson] Materials design theory links properties and microstructure to identify optimized microstructure (orange dot) and to predict the effects of processing pathways (lines) on the physical properties of real starting materials (blue dots) [B. Adams, S. Kalidindi] 40 nm Figure of Merit (ZT) 200 nm Well or Wire Width (Ǻ) Integrated computational models, experimental characterization tools and materials processing efforts guide advanced fiber and fabric designs for unparalleled armor systems [P.M. Cunniff] Materials theory motivated discovery of unprecedented thermoelectric materials with ultra-fine structure for advanced thermal management [M. Dresselhaus, Hicks]

18. 3D MURI(U. Illinois U-C, Stanford, U. New Mexico) Direct writing of polyelectrolyte ink Computationally-guided structure step 1 photonic band gap Brillouin zone Robotically defined woodpile structure step 2 a) SiO2 CVD (25°C) b) Calcine (475°C) woodpile structure Spectroscopy and modeling underway, future iterations of structure and processing for complete photonic band gap material step 4 step 3 Si CVD (475°C) 2 µm 5 µm Si woodpile structure SiO2 replica of polymer woodpile

19. Large-Strain Magnetic SMAs(I. Karaman, Texas A&M University) Strain vs. temperature response of a CoNiAl alloy showing >4% shape memory strain and hysteresis shrinkage Strain vs. magnetic field response of Ni2MnGa demonstrating very large magnetic field induced strain (more than 4.5% in compression) • Simulations predicted extraordinary potential for large force, large strain, and high frequency actuator materials • Induced strains demonstrated up to 4.2% under compression, 10% in tension

20.  p Nanoporous Energy Absorbing Systems(Y. Qiao, U. Akron) Hydrophobic Nanoporous particle Dynamic Testing Results (SHPB) Water Water p NEAS D Gasket Container Piston Strain (%) Surface of the nanoporous silica particle v 2r Time (sec) Nanopore 6-20 nm pore size, 10-12% coverage, ~12 J/g energy absorption • When a non-wetting liquid is forced to flow into nanoporous materials under external pressure, due to the high surface/mass ratio a large amount of energy will be transformed into the solid-liquid interfacial tension • Modeling predicted the energy absorption efficiency of nanoporous systems will be higher than larger systems by an order of magnitude

21. E-field switchable specific binding to surface Bio-HybridsIntegrating Functional, Structural and Biological Materials • Controlled binding • Reconfigurable self-assembly and regeneration • Spatially directed growth of quantum dots and nanoscale coatings • Targeted and controlled drug delivery A genetically driven and universal process for controllable and switchable adhesive materials interfaces

22. Synthetic Active Transport MURI(U. Cincinnati & U. Pittsburgh) OBJECTIVE: To produce synthetic flexible membranes containing biological transport proteins that can utilize energy for the selective uptake, concentration and release of ions and molecules in an organized manner. The effort includes production of both macroscopic membranes and nanostructures containing transport proteins with vectorial transport function. • ACCOMPLISHMENTS: • The first ever functional ion-selective synthetic protein membrane on inorganic support has been prepared and demonstrated, providing unprecedented potential for future sensors, drug delivery, and fuel cells. • Developed enhanced algorithm to predict transport pathways in proteins, even for very large turns; this effort identified 4 possible pathways within the bacterial Cl channel that were later confirmed by experimental evidence. RESEARCH TEAM: University of Cincinnati John Cuppoletti (Physiology and Biophysics) T.L. Beck (Computational+Theoretical Chem.) J. Boerio (Materials Science and Engineering) J.Y.S. Lin (Chemical Engineering) P.R. Rosevear (Biochemistry and Microbiology) University of Pittsburgh R. Coalson (Computational Chemistry+Physics)

23. Self-Healing F-R Composites(M. Kessler, University of Tulsa) Technical Objective: To demonstrate and refine robust self-healing fiber-reinforced composite materials for recovery of micro-cracking and similar small-scale damage. SEM micrograph showing fracture surface of a healed reference plain weave specimen Self healing concept

24. Improving Technology Transfer • Nanomanufacturing to enable scaled-up, reliable, cost effective manufacturing of nanoscale materials, structures, devices, and systems; the development and integration of ultra-miniaturized top-down processes and increasingly complex bottom-up or self-assembly processes. • Small Business Innovative Research (SBIR) • Small Business Technology Transfer (STTR) • Manufacturing Technology (MANTECH) program • Industry partnerships? • Spiral development? • “Preliminary” field testing?

25. david.m.stepp@us.army.milhttp://www.aro.army.mil • Basic Research and the U.S. Army Research Office • Farsighted high-payoff research • Needs driven and opportunity driven basic research efforts • Nanotechnology and Lightweight Materials • Tremendous potential for enhancing functionality • Beware non-falsifiable hypotheses, esp. for mechanical/structural apps. • What’s After Nanotechnology • Optimized Materials Design? • Bio-hybrids? • Improved Technology Transfer