Alabama Center for Nanostructured

Materials (ACNM)

Mahesh V. Hosur, PI/Director

Center for Advanced Materials
Tuskegee University
Tuskegee, AL 36088

Annual EPSCoR 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. Undergrad. High School

Students Students 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 PhD students with 8 of them being

African-Americans, 5PhD students are being supported by the alabama
State Graduate Student Research Program
It is anticipated that at least 5 PhD students will graduate by May 2008
 GSRP Awardees

Ivy K. Jones Wanda D. Jones Merlin Theodore

Jean Michael Taguenang 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 EPSCoR program appeared in Montgomery
advertiser on July 25, 2005:
http://www.montgomeryadvertiser.com/NEWSV5/storyV5tuske
gee25w.htm
 President Bush Visits Tuskegee University
Center for Advanced Materials (T-CAM)-April 19, 2006

“I met some students who knew lot about nanotechnology-PhD 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 (10th 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, electric, 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
2000
Matrix: SC-15 Epoxy 45

Reinforcement: Carbon Nano Fiber

1600

0 wt. %, 1 wt. %, 2 wt. % and 3 wt. %

Storage Modulus (MPa)

Stress (MPa)
1200
Storage Modulus 70% improvement
40

800

Neat Epoxy
1 wt. % CNF
Glass Transition Temp. 7oC increase Neat Epoxy
400
2 wt. % CNF 1wt.% CNF/Epoxy

3 wt. % CNF 2wt.% CNF/Epoxy

0
Tensile Modulus 17.4% improvement 35
3wt.% CNF/Epoxy

0 40 80 120 160 200 100 1000 10000 100000 1000000

o
Temperature ( C) Number of Cycles

80 Tensile Strength 19.4% improvement

1000
2 wt% CNF/Epoxy

3 wt. % CNF/Epoxy
60
1 wt. % CNF/Epoxy Fatigue Performance 800 3% CNF/Epoxy
2% CNF/Epoxy
Stress (MPa)

1% CNF/Epoxy

At the same fatigue stress level, 600 Neat Epoxy

Load (N)
40

Neat Epoxy
140% improvement in fatigue life 400

20 was observed in 2 wt% system by

the bridging effect of CNF 200

0.00 0.01 0.02 0.03 0.04

Fracture toughness 0
Strain
23% increase in fracture toughness 0.00 0.20 0.40
Displacement (mm)
0.60

was observed in 2 wt% system

 Mechanical Properties of
Nanophased Nylon Fibers

With the use of 1% silica spherical 800

nanoparticles by weight, an increase of

100 to 150% in the tensile properties
was observed in nylon-6.
600

It was also observed that the fibers

infused with 1% by weight whisker form of
Si3N4 exhibited more than 300%

stress in MPa
improvement in tensile strength. 400

Aligned
Nano whisker
200

0
0 5 10 15 20 25
Strain in %

TEM picture of Nylon-Si3N4

 Experimental-Flexural Results

500
VARTM results
Fabric: 8-layered plain weave
400
3k, Resin: SC-15 Epoxy,
Flexural stress, MPa

Nanoclay: Nanocor® I-28E

300

200 1%nanoclay
2%nanoclay
3%nanoclay
Neat composite
100

0
0 0.003 0.006 0.009 0.012 Hand-Layup results
Strain, m/m
Flexural stress-strain plot Flexural % Gain/ Flexural % Gain/
Strength, Loss in Modulus, GPa Loss in
MPa strength 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

VARTM
Fabric: 8-layered plain weave 3k, Resin: SC-15 Epoxy, results
Nanoclay: Nanocor® I-28E

Impact Energy: 30J

Sample Damage Area (mm2)
Neat 1144
1% 860

Neat 1% 2% 660
3% 920

2% 3%
 Different Methods of Functionalization

OH
Oxidation HNO3/H2SO4 OH
C C
O
O

Fluorination F F F

F F F

Amino-functionalization

NH2
 Flexural 3-point bend test

Material Max. Strength Modulus

(MPa) (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-NH2 162.8 ± 4.6 4.2 ± 0.1
 Syntactic Foam (TU)

Conventional polymer foams are produced, for example, by introducing gas

bubbles into liquid monomer

Syntactic Foams are produced by embedding pre-formed hollow/solid

microspheres within a polymer matrix

 Microballoons act as cells of the conventional foam

 They are very similar to the cellular, gas expanded solidified liquid
 A tertiary system whereas conventional foams are binary system

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 (3M)
Size: 30-105 µm
Avg. Density: 0.15 g/cc
Avg. wall thickness: 0.7 µm
Nanoparticles Nanoclay- K10 (Sigma Aldrich Inc.)
Shape: Plate type
Avg. surface area: 220-270 m2/g
 Mechanical Properties of Syntactic
Foam (TU)
30

20

Flexural test results of the samples indicate a maximum

Stress, MPa

improvement in strength and modulus of about 42%

Neat sample and 18% respectively for 2 wt % nanoclay system
10 1 wt% Nanoclay
2 wt% Nanoclay
3 wt% Nanoclay

0
0 0.5 1.0 1.5 2.0

Strain, %

Flexural Improvement Flexural Improvement

strength in strength modulus in modulus (%)
(MPa) (%) (GPa)
Neat 17.7 ±0.21 - 1.33 -
sample ±0.039
1 wt% 20.3 ±0.13 14.7 1.50 12.8
Nanoclay ±0.036
2 wt% 25.1 ±0.15 41.8 1.57 18.0
Nanoclay ±0.043
3 wt% 22.8 ±0.11 28.8 1.57 18.0
Nanoclay ±0.035
 Thermal Properties of Syntactic Foam (TU)

0.4
2000 –––––– Neat sample
–––––– Neat sample ––– 1 wt% nanoclay
––– 1 wt% nanoclay –––– · 2 wt% nanoclay
–––– · 2 wt% nanoclay –– – – 3 wt% nanoclay
–– – – 3 wt% nanoclay

0.3
1500
Storage Modulus (MPa)

Tan Delta
1000 0.2

500 0.1

0
20 40 60 80 100 120 140 160 0.0
20 40 60 80 100 120 140 160
Temperature (°C) Universal V3.8B TA Instruments
Temperature (°C) Universal V3.8B TA Instruments

Storage modulus % Change Loss modulus % Change Tg (0C) Change

(MPa) (MPa) (0C)
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 70C increase in glass transition
temperature is observed for 2 wt % nanoclay system
 Thermal Properties of Syntactic Foam (TU)

80
––––––
–––
Neat sample
1 wt% nanoclay
Coefficient of thermal expansion was found
–––– ·
–– – –
2 wt% nanoclay
3 wt% nanoclay using the formula as follows:
60
1 dL
 *
Dimension Change (µm)

40
L dT
20 The slope of the initial portion of the curves
give the value for dL/dT and L is the
thicknesses of the samples
0

-20
20 40 60 80 100 120 140 160 180
Temperature (°C) Universal V3.8B TA Instruments

CTE (µm/m0C) Change

(0C)
TMA results exhibited 70C decrease in
CTE value for 3 wt % nanoclay system 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—BiTe/SbTe Semiconductors
21st Century Technology---Metal/Insulator
nano superlattice

Higher Thermoelectric figure of merit

Approach
ZT=(S2σT)/
Zn4Sb3 / CeFe(4-x)CoxSb12 nano-layered superlattices Figure of Merit (ZT)
Si1-xGe x/Si after Bombardment by 5 MeV Si Ions
Au/SiO2 Metal nano particle superlattice Summary
• 50 to 1000 nanolayers were
produced in house.
Future Plans • Post Irradiation reduced thermal
Produce a prototype high temperature
metal/insulator thermoelectric generator conductivity, increased electrical
for direct energy conversion of waste heat 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

xB
Objective
+V
1

Acceleration Involve undergraduate students

Results
and focusing
in significant nano technology

+V
2
Approach 0.6

1 Produce 10-100 nm metal particles

-V
2 Use ion beam techniques 0.4

-Log ( 1/T )
Pump
for mass separation 43.5 nm

3 Use optical techniques 0.2

Optical absorption spectrum of silver nanoparticles on glass

to characterize size distribution (Obtained by electric arc in normal atmosphere)

Sample 2
Sample 2 immersed in H2O

Future Plans 0.0

300 400 500 600 700
03 November 2006
Electric arc nano Wavelength (nm)
• Continue student involvement in nano
Test009 and 010 Cary 5000

Particle Source
scale technology research Optical evidence of 2-5 nm
• (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 /cm3)
Results
Thermal expansion (zero), Inert (except oxygen)
55

Objectives 50
GPC
Pure GPC
CNT1 wt%
GPC/CNT
10%
To Enhance
45
Composite
GPC/CNT 2 wt%
GPC/CNT 3 wt%
40
GPC/CNT 5 wt% 5%
1 Mechanical properties: Hardness, Stiffness, Strain to fracture 35

Stress (MPa)
GPC/CNT 10 wt%
3%
30
2 Transport properties: Electrical, Thermal, Fluid diffusion 25
2%
3 Biocompatibility 20
1%
15

10
Virgin
5
50 mm 0
0.00 0.05 0.10 0.15 0.20 0.25

Strain (%)
50% Increased strain to failure
300% Increased stiffness
Approach Carbon Nano Tube 10-30 nm
1 CNT: Electrical and Mechanical
2 Al2O3 and SiC, Electrical
Future Plans
3 Ion Beam Surface Modification Technology Transfer
Controlled cell adhesion Aerospace
Controlled porosity Medical
Collaborate closely with carbon Consumer
composite pioneers at Tuskegee University
 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
Flocculation Rate vs. Magnetic Field Density
2
10

1
Flocculation Rate

10

0
10

-1
10
1 2
10 10
Vma1/2
 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 Si3N4, Al2O3, SiC, and TiO2
• 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 2O3.
 ACNM-UAH Effort

Perfluorocyclobutyl (PFCB) optical waveguides with air trenches

(partial support for 2 PhD students)

Measurement of AWG in
Ring Resonator Design with PFCB
Air Trench Splitters
• 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. $100K)
• SBIR Phase I: Advanced Composites Research to Reduce Costs, 6/15/2006, Ondax Inc.
($105K)
• STTR Phase I: Nanocluster characterization in Volume Holographic Glass
gratings,6/25/2006, Ondax Inc. ($105K)

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)