Defense Applications of Nanomaterials - ACS Publications - American

Chapter 1

Overview of the Nanoscale Science and Technology Program in the Department of Defense 1

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J. S. Murday , B. D. Guenther , C. G. Lau , C. R. K. Marrian , J. C. Pazik , and G. S. Pomrenke Downloaded by NORTH CAROLINA STATE UNIV on September 16, 2013 | http://pubs.acs.org Publication Date: January 21, 2005 | doi: 10.1021/bk-2005-0891.ch001

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Department of the Navy, Naval Research Laboratory, 4554 Overlook Avenue, SW, Washington, DC 20375-5320 Department of Physics, Box 90305, Duke University, Durham, NC 27708 DUSD (S&T/BR) Ballston Centre Tower 3, 4015 Wilson Boulevard, Arlington, VA 22203 Defense Advanced Research Projects Agency and Department of the Navy, Naval Research Laboratory, 4554 Overlook Avenue, SW, Washington, DC 20375-5320 Office of Naval Research, Ballston Centre Tower 1, 800 North Quincy Street, Arlington, VA 22217 Air Force Office of Scientific Research, Ballston Centre Tower 3, 4015 Wilson Boulevard, Arlington, VA 22203-1954 2

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The U.S. National Nanotechnology Initiative (NNI) is a coordinated multiagency/department program with the NSF leading the fundamental science investment and the other agencies/departments focused on science investment that promises revolutionary new technologies relevant to their missions. The Department of Defense has identified three nanoscience challenges for focused S&T investments nanoelectronics, magnetics and photonics; nanomaterials; and nanobiodevices. This article will succinctly sketch the reasons for excitement over nanoscience and the DoD program.

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U.S. government work. Published 2005 American Chemical Society

In Defense Applications of Nanomaterials; Miziolek, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

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Introduction Nanoscience involves materials where some critical property is attributable to a structure with at least one dimension limited to the nanometer size scale, 1 100 nanometers . Below that size the disciplines of Chemistry and Atomic/Molecular Physics have already provided detailed scientific understanding. Above that size scale, in the last 50 years Condensed Matter Physics and Materials Science have provided detailed scientific understanding of microstructures. So the nanoscale is the last "size" frontier for materials science. The interest in nanostructures extends beyond their individual properties. We have learned to exploit the natural self-assembly of atoms/molecules into crystals. The directed self-assembly of nanostructures into more complex, hierarchical systems is also an important goal. Without direct self-assembly, manufacturing costs will severely limit the nanotechnology impact. While the scientific understanding of nanostructures is deficient, their use in technology is at least two thousand years old. The Lycurgis cup, a Roman artifact pictured in the lower left of Figure 1, utilizes nanosized Au clusters to provide different colors depending on front or back lighting. The Roman artisans knew how to achieve the effect; they didn't know its nanocluster basis.

Downloaded by NORTH CAROLINA STATE UNIV on September 16, 2013 | http://pubs.acs.org Publication Date: January 21, 2005 | doi: 10.1021/bk-2005-0891.ch001

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Figure 1. Paleontology ofNanostructures (See page 1 of color insert.)



4 In the last century nanostructures have contributed to many significant technologies - examples include the addition of nanosized carbon particles to rubber for improved mechanical properties (tires) and the use of nanosized particles for catalysis in the petrochemical industries. These technologies were all developed empirically. As depicted in Figure 1, one might assign these examples to an empiric epoch in the continuing evolution of nanotechnology. Empirically based technology, without greater scientific understanding, is usually difficult to extend or control. Since the Department of Defense demands the highest performance from its systems, it is always looking to enhance material properties and to minimize their failure mechanisms. So there is a strong DOD interest in nanoscience. The scientific foundation of nanostructures received a quantum advance when surface science enjoyed a renaissance starting in the 1960s. Surface science constrained one material dimension into the nanometer size scale. Events catalyzing that renaissance were the development of new surface-sensitive analytical tools, the ready availability of ultra-high vacuum (a by-product of the space race), and the maturity of solid-state physics (surfaces representing a controlled lattice defect - termination of repeating unit cells). The principal economic driving force was the electronics industry. From 1960 to now, surface science has progressed from "clean, flat and cold" into thin films (two or more nanoscale interfaces) and film processing. Superlattice devices (see Figure 2) are a growing technological manifestation where the individual layers are nanometer in thickness and the interfaces are controlled with atomic precision.

Figure 2. Superlattice-based Commercial Devices (See page 1 of color insert) In Defense Applications of Nanomaterials; Miziolek, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

5 If nanotechnology has been around so long, why is it the current rage? The 1990s nanoscience renaissance has close parallels to the 1960 surface science renaissance. First, beginning in 1980, the discovery and development of proximal probes - scanning tunneling microscopy/spectroscopy, atomic force microscopy/spectroscopy, near-field microscopy/spectroscopy - have provided tools for measurement and manipulation of individual nanosized structures . Those tools needed 10-15 years for reliable commercial instruments to come onto the markets. Note the rapid increase in refereed nanoscience publications beginning in the early 1990s (see Figure 3). The properties of the individual nanostructures can now be observed, rather than the ensemble averaged values. In turn, those properties can be understood in terms of composition / structure, with that understanding comes the possibility for control, and with control comes the possibility for accelerated progress toward new technology. Second, in addition to the new experimental measurement capabilities, computer hardware is now sufficiently advanced (speed and memory capacity) such that accurate predictions, even first principle, are enabled for the number of atoms incorporated in a nanostructure (see Table I). Accurate predictions for carbon nanotubes were made years before experimental measurements could confirm their validity. Modeling and simulation will play a leading role in the race toward nanotechnology.


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4 STMAFM REFEREED JOURNAL ARTICLES -H

• NANOTECH PATENT *

Jfc-fL

1911 1112 1113 1W4

IftS lltf

1117

• • IfII 1919 If10

1991 1992 1993 1994 199S 19M 1997 1991 1999 2WI 2011 2112 2083

"Nanotethitology ~ Size Matters", white paper, 10 Jiily 2002, Institute of Nanoteflutology

Figure 3. Annual Publication Count



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Table I. Carbon Nanotubes: Prediction and Subsequent Confirmation

Prediction

Experimental Confirmation 4

Armchair SWNTs metallic.

Individual single-wall carbon nanotubes as quantum wires.

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Elastic modulus should be similar to high stiff-ness in-plane modulus of graphite. 6

Nanobeam Mechanics: Elasticity, Strength, and toughness of Nanorods and graphite Nanotubes. 7

Stability of metallic SWNT conduction Fabry-Perot interference in a nanotube channels in presence of disorder, electron wave-guide. leading to exceptional ballistic transport properties. 9

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7 NANOMETER SCIENCE AND TECHNOLOGY:


CONFLUENCE OF PHYSICS, CHEMISTRY, AND BIOLOGY

1950

1960

1970

1980

1990

2000

2010

YEAR

Figure 4. Convergence of biology, chemistry, and physics at the nanoscale.

Third, the disciplines of biology, chemistry, materials, and physics and have all reached a point where nanostructures are of interest - chemistry building up from simpler molecules, physics/materials working down from microstructures, and biology sorting out from very complex systems into simpler subsystems (see Figure 4). If one expected to simply extrapolate the properties of nanostructures from the size scales above or below, then there would be little reason for the current interest in nanoscience/nanotechnology. There are three reasons for nanostructured materials to behave very differently: large surface/interface to volume ratios, size effects (where cooperative phenomena like ferromagnetism is compromised by die limited number of atoms/molecules) and quantum effects. Many of the models for materials properties at the micron and larger sizes have characteristic length scales of nanometers (see Table II). When the size of the structure is nanometer, those parameters will no longer be adequate to model/predict the property. One can expect "surprises" - new materials behavior that may be technologically exploitable.


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Table II. Characteristic Lengths in Solid State Science Models

ELECTRONIC

ELECTRON WAVELENGTH INELASTIC M E A N FREE PATH TUNNELING

SCALE LENGTH 10 - lOOnm 1 - lOOnm 1 -lOnm

MAGNETIC

DOMAIN WALL EXCHANGE ENERGY SPIN-FLIP SCATTERING LENGTH

10 - lOOnm 0.1 - lnm 1 - lOOnm

OPTIC

QUANTUM WELL EVANESCENT WAVE DECAY LENGTH METALLIC SKIN DEPTHS


FIELD

PROPERTY

SUPERCOOPER PAIR COHERENCE CONDUCTIVITY LENGTH MEISSNER PENETRATION DEPTH MECHANICS

DISLOCATION INTERACTION GRAIN BOUNDARIES

NUCLEATION/ GROWTH

DEFECT SURFACE CORRUGATION

CATALYSIS

LOCALIZED BONDING ORBITALS SURFACE TOPOLOGY

SUPRAMOLECULES

PRIMARY STRUCTURE SECONDARY STRUCTURE TERTIARY STRUCTURE

IMMUNOLOGY

MOLECULAR RECOGNITION

1 - lOOnm 10 -- lOOnm 10-1 OOnm 0.1 - lOOnm 1 - lOOnm 1 - lOOOnm 1 - lOnm 0.1 - lOnm 1 - lOnm 0.01 -O.lmn 1 - lOnm 0.1 - lnm 1 - lOnm 10 - lOOOnm 1 -lOnm



9 Finally, there are several economic engines driving the interest with information technology (electronics), biotechnology (pharmaceuticals, healthcare, and agriculture), and high performance materials the more certain beneficiaries. Several estimates have been made for the economic impact of nanotechnology. They all cite a worldwide commercial market on the order of $1T per year by 2020 for systems whose function is enabled by the properties of nanostructures - "Nano Inside." With these substantial scientific and economic opportunities, it not surprising to find strong global interest in fostering nanoscience, with the intent of accelerating scientific discovery into innovative commercial product. The increasing nanotechnology patent literature shown in Figure 3 gives evidence for that acceleration. Table III has an estimate of governmental funding in the nanosciences around the globe. From estimates of FY03 budget projections, it is anticipated that well over $3B will be invested in nanotechnology S&T in 2003, with the U.S. contribution around $850M, and the DOD contribution around $300M. One should be careful in the comparison of funding levels between different countries. For instance, one estimate of nanotechnology investment in China is around $25M/year; however, the manpower costs in China are significantly less than in the U.S. and that investment is not so small as it might seem.

US National Nanotechnology Initiative The U.S. response to the nanoscale scientific and economic opportunities is the National Nanotechnology Initiative (NNI), recently enacted into law by the 108 Congress as the "21st Century Nanotechnology research and Development Act." An outline of the funding categories in the NNI is provided below (for more details see National Nanotechnology Initiative, detailed technical report th

Table III. "Nanotechnology" Research Program Investment ($M) 1997

2000

2001

2003

USA

115

270

420

-800

Japan

120

245

410

-800

Western Europe

125

200

225

-700

Other Countries (FSU, China, Australia, others)

70

110

200

-800

Total

430

749

1230

>3000


10 associated with the supplemental report to the President's FY2004 Budget Table IV shows the annual investment levels in nanoscience:


Table IV. U.S. National Nanotechnology Initiative Program ($M) Category Knowledge Generation Grand Challenges Nanostructured Materials by Design Nanoelectronics, Photonics, Magnetics Advanced Healthcare/Therapeutics Environmental Improvements Energy Conversion/Storage Microcraft and Robotics CBRE Protection/Detection Instrumentation & Metrology Nanoscale Manufacturing Centers/Networks Infrastructure Ethical/Social Implications Totals

Lead

FY00 87 71

FY01 140 125

47 50 15 270

66 77 21 422

NSF DOD NIH EPA DOE NASA DOD NIST NSF

FY03 230 400 -120 -110 -60 -10 -10 -5 -20 -50 -10 130 90 16 -860

The Knowledge Generation investment is deliberately broad based. Science discovery frequently occurs in unexpected ways; it is important to have part of the investment portfolio available to give breadth and depth to the range of nanoscience projects. In the Grand Challenges, the research investments are selected with technological ramifications in mind. The lead agency has the responsibility for surveying the investment in the designated Grand Challenge and for identifying investment opportunities/shortfalls. Most of the Grand Challenge topics have been the subject of a recent workshop; copies of the workshop reports can be obtained from the NNI website (www.nano.gov).

DoD contributions to Nanoscale Science and Engineering The DoD has been investing in fundamental nanoscience research for over 20 years. As examples: a) one of the early programs, dating into the early 1980s was Ultra-submicron Electronics Research (USER); b) ONR initiated an accelerated research initiative (ARI) in Properties of Interfacial Nanostructures in 1990; c) ARO initiated a nanoscience University Research Initiative (URI) in 1991; and d) DARPA initiated the ULTRA (ultra dense, ultra fast computing) program in 1991. In 1997 the DoD identified several S&T topics with the


11 potential for significant impact on military technology; nanoscience was selected as one of those special research area (SRA) topics. Selected examples of anticipated impact are listed in Table V. A website and coordinating committees have been established, and each Service has its own laboratory nanoscience programs. 11


Table V. Nanoscale Opportunities with Major DoD Impact Nanoelectronics/Optoelectronics/Magnetics Network Centric Warfare Information Warfare Uninhabited Combat Vehicles Automation/Robotics for Reduced Manning Effective training Through Virtual Reality Digital Signal Processing and LPI Nanomaterials "by Design" High Performance, Affordable Materials Energetic Materials and Controlled Release of Energy Multifunction Adaptive (Smart) Materials Nanoengineered Functional Materials (Metamaterials) Reduced Maintenance (halt nanoscale failure initiation) BioNanotechnology - Warfighter Protection Chemical/Biological Agent detection/Destruction Human Performance/Health Monitor/Prophylaxis

While the NNI is an initiative focused on fundamental science (i.e., DoD 6.1 funding category), one of the principal NNI goals is to transition science discovery into new technology. The DoD structures its S&T investment into basic research (6.1), applied research (6.2) and exploratory development (6.3); the latter two focus on transitioning science discovery into innovative technology. MANTECH, SBIR and STTR programs are also available for transition efforts. There are nanoscience discoveries for which technology potentials are clear and transition funding is appropriate. Beginning in FY02, the DoD is tracking and encouraging the transitions into these applied programs. They are included under the label "6.2/6.3" in Table VI.


12 Table VI. DoD Investment in Nanoscience

Total

1998 2000 6.1 6.1 73 90

6.1 121

2001 6.2/6.3 32

2002 6.1 6.2/6.3 141 84

2003 6.1 6.2/6.3 179 143

The Air Force is increasing its investment in nanoscience with a NAS panel report as guidance . The Air Force basic research activities address topics in: - Nanocomposites- hybrid polymer-inorganic nanocomposites for dramatic improvement over the properties of traditional polymers without sacrificing density, processability or toughness as in conventional composite/blend approaches; dispersed carbon nanotubes in polymer fiber to provide improvement in tensile and compressive properties of high performance polymer fibers. - Self-assembly and Nanoprocessing - advances in organic and organic/inorganic nanoparticles and nanoscale materials and nanoscale materials processing techniques to create the opportunity for development of new paradigms for the realization of 3-D optical and electronic circuitry. - Highly Efficient Space Solar Cells - if U.S. satellites could be developed which more efficiently convert light to electrical power, then lower launch costs and heavier payloads could be realized. Nanotechnology may enable space solar cells that can operate at an efficiency of 60%. - Nanoenergetics - understanding the factors that control reactivity and energy release in nanostructured systems, and developing the structures and architectures to optimize them. - Nanostructures for Highly Selective Sensors and Catalysts nanostructures for the remote sensing and identification of chemical and physical species, and catalysts to selectively react with compounds to release energy (monopropellants) or destroy them (undesirable chemicals). - Nanoelectronic Nanomagnetics and Nanophotonics - ultra-dense magnetic memory, ultra-fast digital signal processing, nanosensing, spatial and temporal dispersion characteristics of photonic crystals, and a computer architecture based on one-dimensional cellular automata which offers an important solution to molecular scale limitations. - Nanostructured coatings, ceramics and metals - tailor the structure of coatings at the nano-scale to provide unique and revolutionary properties, specifically nano-structured adaptive tribological (low friction) coatings for MEMS devices; economical, multifunctional ceramic materials to which operate in extreme environments; new material concepts and design tools to impact mechanics issues important to airframes. The Army is augmenting its program with a University Affiliated Research Center (UARC) - Institute for Soldier Nanotechnologies. The purpose of this center of excellence is to develop unclassified nanometer-scale science and technology solutions for the soldier. MIT hosts this center, which will emphasize


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13 revolutionary materials research toward advanced soldier protection and survivability capabilities. The center works in close collaboration with industry, the Army's Natick Soldier Center (NSC), the Army Research Laboratory (ARL) and the other Army Research Development and Engineering Centers (RDECs) in pursuit of the Army's goals. The research will integrate a wide range of functionalities, including multi-threat protection against ballistics, sensory attack, chemical and biological agents; climate control (cooling, heating, and insulating), possible chameleon-like garments; biomedical monitoring; and load management. In addition, the Army has just created a second UARC entitled Institute for Collaborative Biotechnology at the University of California, Santa Barbara; this center will also seek to exploit nanoscale phenomena. The Navy investment in nanotechnology has an emphasis in the area of nanoelectronics. Reprogramming $10M of its core funds, the Naval Research Laboratory has initiated an Institute for Nanoscience to enhance multidisciplinary thinking and critical infrastructure. The mission of the institute is to conduct highly innovative, interdisciplinary research at the intersection of the fields of materials, electronics and biology in the nanometer domain. A new Nanoscience Building has been constructed at NRL to provide modem, state-ofthe art facilities dedicated to nanoscience research and nanotechnology development. The building has been specially designed and built to minimize sources of measurement noise (acoustic, vibration, electromagnectic, contamination, temperature/pressure fluctuation, electrical power).

Conclusion Nanoscience shows great promise for arrays of inexpensive, integrated, miniaturized sensors for chemical / biological / radiological / explosive (CBRE) agents, for nanostructures enabling protection against agent, and for nanostructures that neutralize agents . The recent terrorist events motivate accelerated insertion of innovative technologies to improve the national security posture relative to CBRE. The NNI has redefined a Grand Challenge to address this important topic; DoD expects to play a major role in this multiagency effort. DoD programs in nanoscience are major contributors to the NNI with the expectation of significant technology innovations for national security and homeland defense. The articles in this book illustrate the breadth and quality of those programs. An Advanced Materials and Processing Technology Information Center (AMPTIAC) Newsletter provides a succinct summary of many DOD programs, and their accomplishments and expectations. 13

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14 References: 1. IWGN Workshop Report: Nanotechnology Research Directions, M.C. Roco, R.S. Williams and P. Alivisatos Eds., (Kluwer Academic Publishers, ISBN 0-7923-62220-9, 2000). 2. Nanotechnology: A Gentle Introduction to the Next Big Idea, Mark A. Ratner and Daniel Ratner, (Prentice Hall PTR; ISBN 0131014005, 2002). 3. Scanning Probe Microscopy and Spectroscopy: Methods and Applications, R. Wiesendanger (Cambridge University Press, ISBN 0-521-41810-0, 1994). Downloaded by NORTH CAROLINA STATE UNIV on September 16, 2013 | http://pubs.acs.org Publication Date: January 21, 2005 | doi: 10.1021/bk-2005-0891.ch001

4. Mintmire, Dunlap, White, PRL 68, 631 (1992) 5. Tans, et.al. Nature 386, 474 (1997) 6. Robertson, Brenner, Mintmire, PRB 45, 12592 (1992) 7. Wong, Sheehan, and Lieber, Science 277, 1971 (1997) 8. White, Todorov, Nature 393, 240 (1998) 9. Liang et. al., Nature 411, 665 (2001) 10. http://nano.gov/nsetrpts.htm 11. http://www.nanosra.nrl.navy.mil 12. Implications of Emerging Micro and Nanotechnologies (National Academy Press, ISBN 0-309-08623-X, 2002). 13. Nanotechnology and Homeland Security, Daniel Ratner and Mark A . Ratner, (Prentice Hall PTR; ISBN 1-13-145307-6, 2002) 14. " A Look Inside Nanotechnology," AMPTIAC Quarterly, Volume 6, Number 1, Spring 2002, ITT Research Institute/AMPTIAC, 201 Mill Street, Rome, N.Y., 13440-6916


Defense Applications of Nanomaterials - ACS Publications - American

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