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.
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 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
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 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
Eric Rousell, Jr.
Selma Early College High School (10th grade)
Future Career: Aerospace or Marine
Engineering
Summer 2006 High School Students
with their mentors
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
Matrix: SC-15 Epoxy
Reinforcement: Carbon Nano Fiber
0 wt. %, 1 wt. %, 2 wt. % and 3 wt. %
Storage Modulus (MPa)
1600
Storage Modulus 70% improvement
1200
800
45
Stress (MPa)
2000
40
Glass Transition Temp. 7oC increase
Neat Epoxy
1 wt. % CNF
Neat Epoxy
400
1wt.% CNF/Epoxy
2 wt. % CNF
2wt.% CNF/Epoxy
3 wt. % CNF
Tensile Modulus 17.4% improvement
0
0
40
80
120
160
o
3wt.% CNF/Epoxy
35
200
100
Temperature ( C)
1000
10000
100000
1000000
Number of Cycles
Tensile Strength 19.4% improvement
80
1000
2 wt% CNF/Epoxy
3 wt. % CNF/Epoxy
Fatigue Performance
60
3% CNF/Epoxy
800
2% CNF/Epoxy
1% CNF/Epoxy
At the same fatigue stress level,
140% improvement in fatigue life
was observed in 2 wt% system by
the bridging effect of CNF
40
Neat Epoxy
20
0
0.00
0.01
0.02
Strain
0.03
0.04
Load (N)
Stress (MPa)
1 wt. % CNF/Epoxy
Fracture toughness
23% increase in fracture toughness
was observed in 2 wt% system
Neat Epoxy
600
400
200
0
0.00
0.20
0.40
Displacement (mm)
0.60
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.
800
It was also observed that the fibers
infused with 1% by weight whisker form of
Si3N4 exhibited more than 300%
improvement in tensile strength.
stress in MPa
600
400
Aligned
Nano whisker
200
0
0
5
10
15
Strain in %
TEM picture of Nylon-Si3N4
20
25
Experimental-Flexural Results
VARTM results
Flexural stress, MPa
500
Fabric: 8-layered plain weave
3k, Resin: SC-15 Epoxy,
Nanoclay: Nanocor® I-28E
400
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
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 3k, Resin: SC-15 Epoxy,
Nanoclay:
Nanocor® I-28E
VARTM
results
Impact Energy: 30J
Sample
Neat
2%
1%
3%
Damage Area (mm2)
Neat
1144
1%
860
2%
660
3%
920
Different Methods of Functionalization
Oxidation
HNO3/H2SO4
OH
OH
C
C
O
O
Fluorination
F F F
F F F
Amino-functionalization
NH2
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-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
Stress, MPa
20
Neat sample
1 wt% Nanoclay
2 wt% Nanoclay
3 wt% Nanoclay
10
0
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
0
0.5
1.0
1.5
2.0
Strain, %
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)
0.4
2000
––––––
–––
–––– ·
–– – –
Neat sample
1 wt% nanoclay
2 wt% nanoclay
3 wt% nanoclay
0.3
Tan Delta
1500
Storage Modulus (MPa)
––––––
–––
–––– ·
–– – –
Neat sample
1 wt% nanoclay
2 wt% nanoclay
3 wt% nanoclay
1000
500
0.2
0.1
0
20
40
60
80
100
120
140
Temperature (°C)
0.0
160
20
40
60
Universal V3.8B TA Instruments
80
100
120
Temperature (°C)
140
160
Universal V3.8B TA Instruments
Storage modulus
(MPa)
% Change
Loss modulus
(MPa)
% Change
Tg (0C)
Change
(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
––––––
–––
–––– ·
–– – –
Coefficient of thermal expansion was found
using the formula as follows:
Neat sample
1 wt% nanoclay
2 wt% nanoclay
3 wt% nanoclay
1 dL
 *
L dT
Dimension Change (µm)
60
40
The slope of the initial portion of the curves
give the value for dL/dT and L is the
thicknesses of the samples
20
0
-20
20
40
60
80
100
120
140
Temperature (°C)
TMA results exhibited 70C decrease in
CTE value for 3 wt % nanoclay system
160
180
Universal V3.8B TA Instruments
CTE (µm/m0C)
Change
(0C)
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
Approach
Higher Thermoelectric figure of merit
ZT=(S2σT)/
Zn4Sb3 / CeFe(4-x)CoxSb12 nano-layered superlattices
Si1-xGe x/Si after Bombardment by 5 MeV Si Ions
Au/SiO2 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
xB
1
+V
Results
Involve undergraduate students
in significant nano technology
2
+V
-V
Pump
Electric arc nano
Particle Source
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
0.6
0.4
-Log ( 1/T )
Acceleration
and focusing
43.5 nm
0.2
Optical absorption spectrum of silver nanoparticles on glass
(Obtained by electric arc in normal atmosphere)
Sample 2
Sample 2 immersed in H2O
0.0
300
400
500
600
700
• Continue student involvement in nano
Optical evidence of 2-5 nm
scale technology research
silver nano particle production
• (Nano particles for innovative solar
cells)
• Work with Tuskegee University for tests
of carbon composites with nano
particle additives
Wavelength (nm)
03 November 2006
Test009 and 010 Cary 5000
Glassy Polymeric Carbon Composites
AAMU
High Temperature (3000 °C), Low Density (1.45 /cm3)
Thermal expansion (zero), Inert (except oxygen)
55
GPC
CNT
GPC/CNT
1 wt%
GPC/CNT 2 wt%
Composite
GPC/CNT 3 wt%
Pure GPC
50
45
40
Stress (MPa)
Objectives
To Enhance
1 Mechanical properties: Hardness, Stiffness, Strain to
fracture
2 Transport properties: Electrical, Thermal, Fluid diffusion
3 Biocompatibility
Results
10%
5%
3%
GPC/CNT 5 wt%
GPC/CNT 10 wt%
35
30
2%
1%
25
20
15
Virgin
10
5
50 mm
0
0.00
0.05
0.10
0.15
0.20
Strain (%)
Approach
Carbon Nano Tube
1 CNT: Electrical and Mechanical
2 Al2O3 and SiC, Electrical
3 Ion Beam Surface Modification
Controlled cell adhesion
Controlled porosity
Collaborate closely with carbon
composite pioneers at Tuskegee University
0.25
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
Flocculation Rate vs. Magnetic Field Density
2
Flocculation Rate
10
1
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)
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. $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)