Assembly, Characterizations, & Applications · 2008-07-21 · Polymer Chain Behavior Outstanding...
Transcript of Assembly, Characterizations, & Applications · 2008-07-21 · Polymer Chain Behavior Outstanding...
NANOCOMPOSITE THIN FILMS:Assembly, Characterizations, & Applications
Chaoyang Jiang
Department of Chemistry
The University of South Dakota
St. Louis, June 26, 2008
Forest Products &Nanocomposite
P. Monteiro@UC Berkeley
Nanocomposite Materials
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Synthesis Composite
Poly(Styrene-butadiene-styrene) (SBS)offers many of the properties of natural rubber, such as flexibility, high traction, and sealing abilities, with increased resistance to heat, weathering, and chemicals.
Wood Fiber
S. Renneckar et.al.Cellulose, 2008, 15, 333.
Nanocomposite Materials
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Nanotechnology R&D Priority for the forest product
NANOCOMPOSITE THIN FILMS:Assembly, Characterizations, & Applications
Layer‐by‐Layer Assembly
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Spin assisted LbL
G. Decher, et al.Science 1997, 277, 1232.
K. Char, et al. Adv. Mater. 2001, 13, 1076.H.-L. Wang, et al. Adv. Mater. 2001, 13, 1167.
J. B. Schlenoff et al. Langmuir 2000, 16, 9968.
Spray assisted LbL
Layer‐by‐Layer Assembly
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Rubner and Cohen
MITCEN, 2005, 83(38), 34.
Kotov, U MichiganNature Mater. 2003, 2(6), 413.
Saraf
U Nebraska Science, 2006, 312, 1501.
Layer‐by‐Layer Assembly
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Cellulose Nanowire (from Tunicate), 3-4 nm, CNW/PEI LbL films, Antireflective properties
Kotov et.al. Langmuir 2007, 23, 7901.
Layer‐by‐Layer Assembly
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Employ cellulose microfibers as a support to fabricate bioactive composites with organized enzyme multilayer.
The bio activity can be tuned by varying the number of enzyme layers.Lvov et.al. Biomacromolecules 2007, 8, 1987.
calcium carbonate
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C. Jiang et al., Nature Mater.. 2004, 3(10), 721.
S. Markutsya, et al. Adv. Funct. Mater., 2005, 15(5), 771
Composite LbL Nanomembrane
Free‐standing LbL Films
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b1
b2
c1 c2
a1
a2
a4
a3
c1 c2
C.Jiang, et.al. Adv. Mater. 2006, 18, 829.
Y. G. Guo, et. al., Adv. Funct. Mater.2005, 15, 196.
V. Kozlovskaya, et.al., Macromolecules
2005, 38, 4828.
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Biomimetic Approach
un-cooled biological receptors with 30mK sensitivity
MembraneIR radiation
Temperature modulatedpressure
Golay cell design of IR detector
V. V. Tsukruk, et al.Biomacromolecules, 2001, 2, 304.
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Sacrificial LayerAcetone
Sacrificial Layer method
Spin-assisted LbLFreely Suspended LbL
nanomembranes
Free‐standing LbL Thin Films
Free‐standing LbL Thin Films
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0 4 8 120
20
40
60
80
Thic
knes
s (n
m)
Number of PAH-PSS bilayers
(PAH-PSS)nPAH/Au/(PAH-PSS)nPAH+ - + - + - +
2 nm
nGnn = 3, 5, 7, 9, 11, …
C. Jiang, et al.Nature Mater. 2004, 3, 721.
Nanomechanics ‐‐ Bulging Tests
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Range accuracyDeflection: 0-10 μm, ½ λ (~300 nm)Pressure: 100 kPa, 2 Pa
Pressuresensor
Laser
CCD Camera
SEM
C. Jiang, et al. Nature Mater. 2004, 3, 721.
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Membrane deflection
Bulging Test
200 μm
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Bulging results and elastic modulus
With Gold
Without Gold
3
4
4
22
20
14
4
20 11⎟⎠⎞
⎜⎝⎛
−+⎟
⎠⎞
⎜⎝⎛
⎥⎦
⎤⎢⎣
⎡+
−=
hd
ahEC
hd
ahC
ahECP
νσ
ν
Mechanical parameters for different freely suspended nanomembranesMembrane type and Gold content
Fabrication method
Membrane diameter(μm)
Elastic modulus(GPa)
9G9, 3.9% SA-LbL 400 6.6±3.39G9, 0.5% SA-LbL 400 4.3±2.09_9 , 0% SA-LbL 400 1.5±1.09G9, 4% LbL N/A * N/A** Film was broken into small piece, which can not be transfer to holey substrate.
C. Jiang, et al. Nature Mater. 2004, 3, 721.
400 μm
Bulging Test
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Micropattern in Nanomembrane
Au NP
C. Jiang, et al. Adv. Mater. 2005, 17, 1669.
Gold Nanoparticle Arrays
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13 nm
1 μm 1 μm
6 nm
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Localized Mechanical Testing
C. M. Stafford, et al. Nature Mater. 2004, 3, 545.A. Nolte, et al. Macromolecules 2005, 38, 5367.
C. Jiang, Nano Letters. 2006, 6, 2254.
30 μmLocation λ (μm) E (GPa)
With Gold 3.52 4.35Without Gold 2.76 2.08
10 μm
Elastic modulus
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SERS in Nanomembranes
PressureSensor
Pump
Sealedchamber
50/50Beam
splitterNotchfilter
Laser
CCD
Nanomembrane
C.Jiang, et al. Adv. Mater. 2005, 17, 1669.
nSO3
-Na+
Confocal Raman microscope
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0 2000 4000 60001580
1582
1584
1586
1588
1590
1592
Ram
an s
hift
(cm
-1)
Deflection (nm)
1 2 3 4 5
1100 1200 1300 1400 1500 1600 1700
1500
2000
2500
3000
3500
4000
80604020
5
0
Rel
ativ
e in
tens
ity
Raman shift (cm-1)
SO3
SO3
SO3
SO3SO3
SO3
SO3
SO3
SO3 SO3
SO3
SO3SO3
SO3
SO3
SO3SO3
SO3
SO3
SO3
SO3
SO3
SO3 SO3SO3
SO3
SO3
SO3
SO3
SO3SO3SO3
SO3
SO3
SO3
SO3
SO3
SO3SO3
SO3
SO3
SO3
SO3
SO3
SO3
SO3
SO3SO3
Polymer Chain Behavior
Outstanding mechanical properties of SA-LbL films
Chain-like Au-NP aggregation + spreading of polymer chains
Bridging multiple nanoparticles through stretched backbones
C.Jiang, et al.Phys. Rev. Lett. 2005, 95, 115503.
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LbL film with Silver Nanowires
2.5%
15.0%
R. Gunawidjaja, Adv. Funct. Mater. 2006, 16, 2024.
Density of Silver nanowires can tune the mechanical properties of LbL thin films.
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Buckling patterns “stop” at the location where silver nanowire appears.
Buckling Patterns of Ag LbL Films
5 μm 20 μm
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3D NanomembranesMicro-sculptured nanomembranes
< 200 nm
Optical Grading with 3D Nanofilm
Y. Lin, et. al. Adv.Mater. 2007, 19, 3827.
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Sensitive LbL Composites Films
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0.0
0.5
1.0
1.5
2.0
2.5
0 400 800 1200 1600
average fit
Pressure (Pa)
Def
lect
ion
(μm
) A1 A2 A3 A4
Membrane Diameter
(μm)
Elastic Modulus
(GPa)
200 5.3±0.4
100 5.6±0.2
75 6.3±1.0
50 6.8±1.2
Micromechanical Tests
C. Jiang, et al. Adv. Funct. Mater. 2006, 16, 27.
200μm
A1 A2 A3 A4
B1
C1
D1
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Microcavity Arrays
Half-inch wafer64×64 cavity array
Over 4000 membranes
600μm
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Uniform Thermal Behavior
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298 299 300 301-400
-200
0
200
400
Def
lect
ion
(nm
)
Temperature (K)
Experimental Finite Element Analysis
Thermal Bulging
Finite Element Analysis
180 nm/K
Heat
Cool
Heat
Cool
C.Jiang, et al. Chem. Mater. 2006, 18, 2632.
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Laser
CCDCamera
Light
785 nm50-150 mW
Laser focus to500 μm diameter
NIR Sensing Tests
Applications for Nanofilms
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Develop multilayer ultra-thin membranes with more flexible polyelectrolyte to achieve higher sensitivity.
Increase thermal isolation and design novel substrates for high resolution imaging application.
Using SERS properties and design portable and sensitive chemicaldetector
Infrared detector with ability to detect NIR radiations in different wavelength.
Biological and medical application, eg. drug release and delivery.
Summary
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Layer-by-Layer assemblya versatile method in fabricating multilayer nanomembranes with a variety of nanoscale building blocks, including cellulose nanocrystals and other forest products.
Surface-enhanced Raman spectroscopyMolecular information within the nanoscale composite thin film; confocal technique can provide spatial resolutions for compositenanomembranes
Free-standing LbL nanomembraneswith functional nanostructures are suitable for sensing applications in mechanical, thermal, and optical areas.
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Acknowledgements
Nanoscale Interdisciplinary Research Team (NIRT) Dr. Vladimir V. Tsukruk (GT) (PI)Dr. Zhiqun Lin (ISU)Dr. Nicholas A. Kotov (U Michigan)Dr. Chang Liu (UIUC/NW)Dr. Eugene Zubarev (Rice U)
$$$AFOSR, NASA, NSF, ARO. Forest Product Laboratory
NSF 05-06832Bioinspired Flex Nanomembranes for Multifunctional Microsensors.
Materials Chemistry @USD
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