Assembling Assembling Nanomaterials Nanomaterials Richard W. - - PDF document
Assembling Assembling Nanomaterials Nanomaterials Richard W. Siegel Rensselaer Nanotechnology Center Rensselaer Nanotechnology Center Rensselaer Polytechnic Institute Rensselaer Polytechnic Institute Korea -U.S. NanoForum 14 October 2003
14 October 2003
Rensselaer Nanotechnology Center Rensselaer Nanotechnology Center Rensselaer Polytechnic Institute Rensselaer Polytechnic Institute
Korea
Seoul, Korea
materials
physics biology chemistry
“Those who control materials control technology”
Eiji Kobayashi, Panasonic
Administration
R.W. Siegel, Director
Nanostructures & Nanodevices Nanocomposite Materials Computational Modeling & Design Nanomaterials for Biotechnology Management & Socioeconomic Implications
Founded April 2001 Founded April 2001
U.S. Army
Natick Soldier Center Eastman Kodak National Science Foundation
State of New York
U.S. Department
Sources of Funding for the Rensselaer Nanotechnology Center NSF 33% Other Federal 35% Industry 16% NY State 8% RPI 8%
annual funding ca. $6 million
K-12 Programs Undergraduate Colleges Morehouse Mount Holyoke Smith Spelman Williams Distance-learning Visiting Researchers Industry Partners ABB Albany International IBM Eastman Kodak Philip Morris New York State Rensselaer Polytechnic Institute University of Illinois at Urbana-Champaign
Nanoscale Science and Engineering Center for Directed Assembly of Nanostructures www.rpi.edu/dept/nsec
Founded September 2001 Founded September 2001
http://www.nano.gov/
dispersions dispersions and coatings and coatings high surface high surface area materials area materials consolidated consolidated materials materials functional functional nanodevices nanodevices
nanoscale building blocks
synthesis
atoms layers nanoparticles nanostructured materials and devices
fundamental gateway to the eventual success
assembly
nanotubes
applications in our macroscopic world
Size confinement High surface area Many interfaces
Size confinement High surface area Many interfaces
NSEC research thrust 1 projects
Nanoparticle Synthesis (Benicewicz , Braun, Moore, Siegel)
Phase Behavior of Nanoparticle-Polymer Mixtures (Schweizer, Zukoski)
Polymer Nanocomposites (Lookman, Schadler, Siegel)
nanoparticle fillers (isolated particles, strings, clusters)
nanocomposites Directed Assembly of Nanostructured Materials (Lewis, Schadler, Zukoski)
features 10 nm
1 mm 3-D lattice 1mm
Nanoparticle Nanoparticle-assembled TiO assembled TiO2 microtubes microtubes
1 µm 100 nm
Ma, Siegel, Schadler (2003)
6 µm 350 nm
Nanotube pillars SiO2 islands Si d
Wei, Vajtai, Jung, Ward, Zhang, Ramanath, Ajayan (2002)
Controlled assembly of Controlled assembly of nanotube nanotube arrays arrays
50 µm
Vertical and Horizontal
Funded by ONR and the MARCO Interconnect Focus Center (Collaboration with Motorola)
Carbon nanotube interconnects
2 µm Ajayan, Wei, et al. (2003)
Creating single Creating single-wall nanotube junctions wall nanotube junctions
e-beam welding
Future
Terrones, Banhart, Ajayan et al. (2002)
Funded by the MARCO Interconnect Focus Center
Cathode G l a s s i n s u l a t
MWNT Film Anode
A C B
Si Substrate Al plate
I
Glass Insulator MWNTs (30 micron) Si Substrate Al plate I Glass Insulator MWNTs (30 micron) V Si Substrate Al plate
I
Glass Insulator MWNTs (30 micron) Si Substrate Al plate I Glass Insulator MWNTs (30 micron) V Si Substrate Al plate
I
Glass Insulator MWNTs (30 micron) Si Substrate Al plate I Glass Insulator MWNTs (30 micron) V
Carbon nanotube gas breakdown sensor
Koratkar , Ajayan et al., Nature (10 July 2003)
200 400 600 800 1000 1200 5 0 100 150 200 250 300 350 400 450 500 Potential difference across electrodes (volts) Current discharge (micro -amperes)
Al: Cathode Al: Anode 150 µm Si0 2 Al: Cathode MWNT Film (Anode) 150 µm
200 400 600 800 1000 1200 5 0 100 150 200 250 300 350 400 450 500 Potential difference across electrodes (volts) Current discharge (micro -amperes)
Al: Cathode Al: Anode 150 µm Si0 2 Al: Cathode MWNT Film (Anode) 150 µm
200 400 600 800 1000 1200 5 0 100 150 200 250 300 350 400 450 500 Potential difference across electrodes (volts) Current discharge (micro -amperes)
Al: Cathode Al: Anode 150 µm Al: Cathode Al: Anode 150 µm Si0 2 Al: Cathode MWNT Film (Anode) 150 µm Si0 2 Al: Cathode MWNT Film (Anode) 150 µm
100 150 200 250 300 350 400 450 100 200 300 400 500 600 Discharge Current (micro-amperes) Breakdown Volatge (Volts) He Ar Air CO2 N2 O2 NH3
Attachment of Au Attachment of Au nanoparticles nanoparticles to N to N-doped doped CNTs CNTs
50 nm
H2SO4/HNO
3
gold colloid
n
Functional groups are attached along the lengths and ends of N-doped carbon nanotubes (CNT). These become the sites for selective Au nanoparticle attachment.
Jiang, Eitan , Schadler, Ajayan, Siegel, et al. (2003) Funded by US Army Natick Soldier Center
Polymer Polymer nanocomposites nanocomposites
♦ Control Filler Properties − particle size − shape (spheres, nanotubes…) − interface chemistry/functionality − connectivity
* isolated species * chains * aggregates
−filler volume fraction
Goal: Design composites with tailored properties
Rg > R > d < 1 nm ~ d 2R
Issues:
due to filler
10 20 30 40 50 60 70 80 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
Strain (mm/mm) Stress (MPa) NEAT PMMA PMMA + 5wt% nano-alumina PMMA + 5 wt% micron-size alumina
Comparison between micron Comparison between micron-size and size and nanoscale nanoscale alumina fillers in PMMA alumina fillers in PMMA
Ash, Schadler, Siegel (2002) Ash, Schadler, Siegel (2002)
Mechanical behavior of filled and neat PMMA
c
1 2 3 4 5 20 25 30 35 40
Weight Percent of Refined Al2O
3 in 5wt% Deionized Gel SolutionScratch Width, µm
100 200 300 400 500
Scratch Depth, nm
40 35 30 25 20 0 10 20 30 40 50 500 400 300 200 100 Nano-alumina filled gelatin
50 wt% nano-alumina
16.7 wt% nano-alumina filled gelatin
Scratch depth (µm) Scratch width (µm) Weight % alumina
Chen, Schadler, Siegel, Irvin (2002)
Polymer Polymer nanocomposites nanocomposites – assembly and properties assembly and properties
1 µ m
Hong, Schadler, Siegel, Mårtensson (2002)
SEM of 50 wt% ZnO in LDPE
LDPE / ZnO nanocomposite
Resistivity Resistivity of
ZnO/LDPE /LDPE nanocomposites nanocomposites
Continuous paths Tunneling
Conduction mechanisms: Hong, Schadler, Siegel, Mårtensson (2002)
10 20 30 40 50 10
8
1010 1012 1014 10
16
10
18
10
20
10
22 10 kV/cm
Resistivity (Ω톍 m) ZnO Content (Vol. %)
PE / ZnO nanoparticles (49nm) PE / ZnO micron particles (300nm) PE / ZnO nanoparticles (24nm) PE powder / ZnO nanoparticles (49nm)
Protein-Nanoparticle Composites (Dordick, Schadler, Ajayan)
NSEC research thrust 2 projects
Characterization (Ramanath, Ajayan) Preparation/Synthesis (Ajayan, Crivello) Molecular Modeling (Garde, Redondo) Tissue Engineering/Biosensing (Bizios, Siegel, Dordick) Biorecognition-Driven Self-Assembly (Wong, Lu, Dordick, Siegel)
Potential applications of biocatalytic nanocomposites Potential applications of biocatalytic nanocomposites
Catalysts Chromatographic packings Biocatalytic membranes Non-fouling coatings and paints
Non-clogging drain pipes Implantable medical devices Microelectronics and microfabrication
C O O H H2SO4: HNO
3
3:1 NHS EDAC
Enzyme
NH2
Biofunctionalizing Biofunctionalizing carbon carbon nanotubes nanotubes
Peroxidase
200 nm
Relative chymotrypsin activity 0.0 0.2 0.4 0.6 0.8 1.0 1.2 Relative SBP activity 0.0 0.2 0.4 0.6 0.8 1.0 1.2 C o n t r o l - C T N - N T / C T 1 4 % S o l u t i o n - C T C o n t r o l - S B P N - N T / S B P 18% S o l u t i o n - S B P
Very high intrinsic activity for unrelated enzymes. Indicates a stable and active biocatalyst nanoscale preparation
1000 2000 3000 4000 Osteoblasts Fibroblasts Endothelial Cells
Cell Density (cells/square cm)
Glass (reference substrate) 167 nm grain size alumina 45 nm grain size alumina 24 nm grain size alumina
* * * * *
‡ ‡
Glass (reference substrate)
Webster, Siegel, Bizios (2001) Data for alumina nanoceramic; similar behavior found for
Osteoblast and fibroblast adhesion Osteoblast and fibroblast adhesion
nanophase alumina / PLA alumina / PLA composites composites
1000 2000 3000 4000 30 40 50 100
* ‡ * *
1000 2000 3000 4000 30 40 50 100
* * *
Cell Density (cells/cm 2)
Substrates (% alumina loading)
Values are mean ±SEM; n=3; *p<0.05 (compared to osteoblast adhesion on the respective 100% alumina; Student’s t-test); ‡ p<0.05 (compared to fibroblast adhesion on 100% alumina; Student’s t-test). Osteoblasts Fibroblasts
Conventional Alumina Nanophase Alumina
McManus, Siegel, Bizios (2001)
Ca Ca Ca
Vitronectin
Ca RGD
24 nm grain size
OSTEOBLAST Ca RGD Conventional Alumina
167 nm grain size
OSTEOBLAST
Integrin receptors Integrin receptors
Nanophase Alumina
driven by surface topography
We are now able to create a wide variety
We are learning how to assemble them into useful nanostructured materials Hierarchical systems at the micro-scale and beyond are beginning to be created Society is beginning to benefit from nanoscience and its applications There is much more to come….!
Rensselaer Nanotechnology Center Rensselaer Polytechnic Institute
100 µm
Ajayan, Nugent, Siegel, Wei, Kohler-Redlich, Nature (2000)