Alabama Center for Nanostructured Materials ACNM Mahesh V

Alabama Center for Nanostructured Materials (ACNM) Mahesh V. Hosur, PI/Director Center for Advanced Materials Tuskegee University Tuskegee, AL 36088 Annual EPSCo. R Meeting, Feb. 13, 2007, Huntsville, AL

ACNM Mission/Goals Research, Education, Training and Outreach • • • Synthesize and produce bulk nanocrystalline materials and develop new materials with enhanced thermal, physical and mechanical properties Integrate research and education in the area of Nanotechnology Initiate new, as well as enhance existing partnerships with industry and academia to attract new funding through development of joint proposals Educate and graduate underrepresented students with expertise in the area of Nanotechnology Conduct National and regional workshops, summer high school and undergraduate student internship programs

Personnel University Faculty Grad. Students Undergrad. Students High School Students Tuskegee 5 18 8 8 Alabama A& M 8 4 5 - Auburn 1 1 - - UAH 3 5 1 - USA 1 1 1 - 18 29 15 8 Out of 29 graduate students, 15 are Ph. D students with 8 of them being African-Americans, 5 Ph. D students are being supported by the alabama State Graduate Student Research Program It is anticipated that at least 5 Ph. D students will graduate by May 2008

GSRP Awardees Ivy K. Jones Wanda D. Jones Jean Michael Taguenang Merlin Theodore Bopah Chhay

ACNM Outcomes • • Journal/conference Publications: 64 Presentations at the national and international conferences Organizing and chairing sessions at international conferences M. S. Thesis (5), Undergraduate technical reports Summer high school program Graduate courses in Nanotechnology at TU and USA Participation of students in oral and poster presentation competitions • Increased number of proposals submitted and funded • Publicity – Visit to the center by President Bush, April 19, 2006 – First article of TU EPSCo. R program appeared in Montgomery advertiser on July 25, 2005: http: //www. montgomeryadvertiser. com/NEWSV 5/story. V 5 tuske gee 25 w. htm

President Bush Visits Tuskegee University Center for Advanced Materials (T-CAM)-April 19, 2006 “I met some students who knew lot about nanotechnology-Ph. D candidates who knew lot about nanotechnology” - President Bush, April 19, 2006

Summer High School Program Summer 2006 High School Students with their mentors Eric Rousell, Jr. Selma Early College High School (10 th grade) Future Career: Aerospace or Marine Engineering While in this program, I learned about Material Science and Engineering. We also learned about nanotechnology and how it is being applied in numerous applications in our everyday lives. I learned a lot and would like to come back next year. -----Eric Rousell, Jr.

Collaborations National/Federal Labs: Oak Ridge National Laboratory, National High Magnetic Filed Laboratory, ARL, AFRL, Navy, NRL, ORNL, NASA-MSFC Academia: Cornell, Purdue, Univ. of Delaware, Mississippi State University, Carnegie Mellon Univ. , University of Alabama, Tuscaloosa, Florida State University Industry: Raytheon, Boeing, IBM, USP International: Japanese National Institute for Metals, University of Liverpool

Course Development Nanocomposite Materials (Dr. Rangari, TU with Dr. Anter from FSU, 10 students) • Nanoscale material synthesis, properties and applications • Theory, modeling and simulation studies • Synthesis mechanisms and morphological changes in nanoscale materials systems, as well as the properties of materials at the nanoscale Nanocomposites (Dr. Parker, USA, 16 students) • Dielectric, magnetic, optical and mechanical properties of nanocomposites • Research and analyze published work dealing with applications

Research Themes • Synthesis, Processing, Modeling, Characterization of nanophased fibers, matrices, composites, and sandwich constructions (Tuskegee) • Nano-layered nanoparticles, Glassy Polymeric Composites (Alabama A & M, Tuskegee) • Molecular Dynamic simulations (Auburn) • Modeling and processing of nanoparticles under the influence of magnetic field (Univ. of South Alabama, Tuskegee) • LC Based Chemical and Biological Sensor Using Capacitive Transduction, Integrated Nanophotonics, LC Polar Anchoring Measurements (Univ. of Alabama, Huntsville)

Thermal and Mechanical Properties of CNF/ Epoxy Nanocomposite Matrix: SC-15 Epoxy Reinforcement: Carbon Nano Fiber 0 wt. %, 1 wt. %, 2 wt. % and 3 wt. % Storage Modulus 70% improvement Glass Transition Temp. 7 o. C increase Tensile Modulus 17. 4% improvement Tensile Strength 19. 4% improvement Fatigue Performance At the same fatigue stress level, 140% improvement in fatigue life was observed in 2 wt% system by the bridging effect of CNF Fracture toughness 23% increase in fracture toughness was observed in 2 wt% system

Mechanical Properties of Nanophased Nylon Fibers With the use of 1% silica spherical nanoparticles by weight, an increase of 100 to 150% in the tensile properties was observed in nylon-6. It was also observed that the fibers infused with 1% by weight whisker form of Si 3 N 4 exhibited more than 300% improvement in tensile strength. Aligned Nano whisker TEM picture of Nylon-Si 3 N 4

Experimental-Flexural Results VARTM results Fabric: 8 -layered plain weave 3 k, Resin: SC-15 Epoxy, Nanoclay: Nanocor® I-28 E Hand-Layup results Flexural stress-strain plot Flexural Strength, MPa % Gain/ Loss in strength Flexural Modulus, GPa % Gain/ Loss in modulus Neat 380 ± 3. 3 - 37. 57 ± 0. 77 - 1% Nanoclay 426 ± 10. 81 12. 10 43. 8 ± 2. 13 16. 58 2% Nanoclay 498 ± 12. 81 31. 05 46. 2 ± 0. 81 22. 97 3% Nanoclay 446 ± 8. 95 17. 36 46. 9 ± 1. 22 24. 8

Impact Response Fabric: 8 -layered plain weave 3 k, Resin: SC-15 Epoxy, Nanoclay: Nanocor® I-28 E VARTM results Impact Energy: 30 J Sample Damage Area (mm 2) Neat 1% 2% 1% 3% 860 2% 660 3% Neat 1144 920

Different Methods of Functionalization Oxidation HNO 3/H 2 SO 4 OH O Fluorination OH C C = F F F Amino-functionalization NH 2 = O

Flexural 3 -point bend test Material Max. Strength (MPa) Modulus (GPa) Epon 862 neat 139. 7± 7. 1 3. 5± 0. 08 Nanocomposite/ MWCNT -UNMOD 152. 1 ± 20. 2 4. 1 ± 0. 2 Nanocomposite/ MWCNT -COOH 151. 1 ± 14. 9 4. 8 ± 0. 6 Nanocomposite/ MWCNT -F 136. 1 ± 12. 2 3. 6 ± 0. 0 Nanocomposite/MWCNT-NH 2 162. 8 ± 4. 6 4. 2 ± 0. 1

Syntactic Foam (TU) ØConventional polymer foams are produced, for example, by introducing gas bubbles into liquid monomer ØSyntactic Foams are produced by embedding pre-formed hollow/solid microspheres within a polymer matrix Microballoons act as cells of the conventional foam Ø They are very similar to the cellular, gas expanded solidified liquid Ø A tertiary system whereas conventional foams are binary system Ø PVC Foam (open cell) PVC Foam (closed cell) PUR Foam (closed cell) Syntactic Foam

Manufacturing of Nanophased Syntactic Foam (TU) Matrix SC-15 Epoxy Part A: diglycidylether of bisphenol- A, Part B: Diethelene tri amine (DETA) Viscosity: 300 cps, Density: 1. 09 g/cc Microballons K-15 (3 M) Size: 30 -105 µm Avg. Density: 0. 15 g/cc Avg. wall thickness: 0. 7 µm Nanoparticles Nanoclay- K 10 (Sigma Aldrich Inc. ) Shape: Plate type Avg. surface area: 220 -270 m 2/g

Mechanical Properties of Syntactic Foam (TU) Flexural test results of the samples indicate a maximum improvement in strength and modulus of about 42% and 18% respectively for 2 wt % nanoclay system Flexural strength (MPa) Improvement in strength (%) Flexural modulus (GPa) Improvement in modulus (%) Neat sample 17. 7 ± 0. 21 - 1. 33 ± 0. 039 - 1 wt% Nanoclay 20. 3 ± 0. 13 14. 7 1. 50 ± 0. 036 12. 8 2 wt% Nanoclay 25. 1 ± 0. 15 41. 8 1. 57 ± 0. 043 18. 0 3 wt% Nanoclay 22. 8 ± 0. 11 28. 8 1. 57 ± 0. 035 18. 0

Thermal Properties of Syntactic Foam (TU) Storage modulus (MPa) % Change Loss modulus (MPa) % Change Tg (0 C) Change (0 C) Neat sample 1220 ± 12 - 123. 2 ± 0. 23 - 105 ± 0. 32 - 1 wt% Nanoclay 1497 ± 26 22. 7 145. 6 ± 0. 41 18. 2 109 ± 0. 43 4 2 wt% Nanoclay 1590 ± 21 30. 3 157. 4 ± 0. 82 27. 8 112 ± 0. 19 7 3 wt% Nanoclay 1292 ± 18 5. 9 128. 8 ± 0. 11 4. 5 109 ± 0. 22 4 Storage modulus increased by 30% and also 70 C increase in glass transition temperature is observed for 2 wt % nanoclay system

Thermal Properties of Syntactic Foam (TU) Coefficient of thermal expansion was found using the formula as follows: The slope of the initial portion of the curves give the value for d. L/d. T and L is the thicknesses of the samples CTE (µm/m 0 C) TMA results exhibited 70 C decrease in CTE value for 3 wt % nanoclay system Change (0 C) Neat sample 41. 9 ± 0. 62 - 1 wt% Nanoclay 40. 5 ± 0. 33 -1. 4 2 wt% Nanoclay 39. 7 ± 0. 93 -2. 2 3 wt% Nanoclay 35. 1 ± 0. 39 -6. 8

Thermoelectric Generator (with superlattice nano particles): AAMU Results Objectives Traditional Technology—Bi. Te/Sb. Te Semiconductors 21 st Century Technology---Metal/Insulator nano superlattice Approach Higher Thermoelectric figure of merit ZT=(S 2σT)/ Zn 4 Sb 3 / Ce. Fe(4 -x)Cox. Sb 12 nano-layered superlattices Si 1 -x. Ge x/Si after Bombardment by 5 Me. V Si Ions Au/Si. O 2 Metal nano particle superlattice Future Plans Produce a prototype high temperature metal/insulator thermoelectric generator for direct energy conversion of waste heat Figure of Merit (ZT) • • • Summary 50 to 1000 nanolayers were produced in house. Post Irradiation reduced thermal conductivity, increased electrical conductivity as well as increase Seebeck Coefficient. Thus Figure of Merit increased.

Nano particle production and electro magnetic mass separation: AAMU Neutral Return Mass Selector Objective x. B 1 +V Involve undergraduate students in significant nano technology Acceleration and focusing 2 +V -V Pump Electric arc nano Particle Source Results Approach 1 Produce 10 -100 nm metal particles 2 Use ion beam techniques for mass separation 3 Use optical techniques to characterize size distribution Future Plans • Continue student involvement in nano Optical evidence of 2 -5 nm scale technology research • (Nano particles for innovative solar cells) silver nano particle production • Work with Tuskegee University for tests of carbon composites with nano particle additives

Glassy Polymeric Carbon Composites AAMU High Temperature (3000 °C), Low Density (1. 45 /cm 3) Thermal expansion (zero), Inert (except oxygen) Objectives To Enhance 1 Mechanical properties: Hardness, Stiffness, Strain to fracture 2 Transport properties: Electrical, Thermal, Fluid diffusion 3 Biocompatibility Results GPC CNT Composite 10% 5% 3% 2% 1% Virgin 50 mm Approach Carbon Nano Tube 1 CNT: Electrical and Mechanical 2 Al 2 O 3 and Si. C, Electrical 3 Ion Beam Surface Modification Controlled cell adhesion Controlled porosity Collaborate closely with carbon composite pioneers at Tuskegee University 50% Increased strain to failure 300% Increased stiffness 10 -30 nm Future Plans Technology Transfer Aerospace Medical Consumer

Magnetic Field-Induced Nanoparticle Dispersion (USA) • Good dispersion of heavy metallic nanoparticles (iron oxide) under magnetic field • Development of lab scale magnetic field device • Modeling magnetic field dependence of nanoparticle dispersion • Good agreement between experimental results

Capture Efficiency Vs Magnetic Velocity for different surfactant layer thicknesses Capture efficiency versus (root) magnetic velocity for various thicknesses of the surfactant layer indicating the extent to which the surfactant layer thickness frustrates the process of agglomeration

Summary of Research Activities of Auburn ACNM Team • Study thermal and mechanical properties through molecular modeling and simulation • Model structure and properties of hard ceramic fillers and soft polymer matrix • Modeling of Si 3 N 4, Al 2 O 3, Si. C, and Ti. O 2 • Initiated simulation studies using LAMMPS code developed by Sandia National Lab. (a) (b) Ab initio calculated (a) lattice thermal expansion and (b) elastic constants of Al 2 O 3.

ACNM-UAH Effort Perfluorocyclobutyl (PFCB) optical waveguides with air trenches (partial support for 2 Ph. D students) Ring Resonator Design with Air Trench Splitters Measurement of AWG in PFCB • Nanofabrication of air trenches in PFCB waveguides enables high efficient, extremely compact planar optical components • Fabricated smallest arrayed waveguide (AWG) utilizing nano-patterned air trench reflector • Fabricated a compact ring resonator utilizing nano-patterned air trench splitters

Integrated Nanophotonics Nanophotonic wave structure significantly reduces waveguide loss New waveguide allows meter propagation distance propagation rather than mm

Proposal Submission Funded Grants: ($3. 985 M) • • • A Research and Educational Partnership in Nanomaterials between Tuskegee University and Cornell University, 8/1/06 -7/31/11, ($2. 55 M with $2. 1 M TU share) Enhancement of Research Infrastructure in the Materials Science and Engineering Program at Tuskegee University, 9/1/06 -8/31/08, ($1. 0 M) Characterizations of Nanocomposites and Composite Laminates, Air Force/HBCU/MI program 8/1/05 -7/31/07 ($225 K, subcontract from Clarkson Aerospace, Inc. ) Modeling High-rate Material Responses for Impact Applications, 11/1/05 -10/31/06 (subcontract from Mississippi State Univ. $100 K) SBIR Phase I: Advanced Composites Research to Reduce Costs, 6/15/2006, Ondax Inc. ($105 K) STTR Phase I: Nanocluster characterization in Volume Holographic Glass gratings, 6/25/2006, Ondax Inc. ($105 K) Other non funded proposals • • $ 881 K (TU being prime) $ 18. 35 M (with Mississippi State and Florida Atlantic with TU share of $2. 05 M)