FUNCTIONAL NANOSTRUCTURED POLYMER - METAL …mcd18:... · 2014. 1. 28. · July 23, 2008 1 Demirel...
Transcript of FUNCTIONAL NANOSTRUCTURED POLYMER - METAL …mcd18:... · 2014. 1. 28. · July 23, 2008 1 Demirel...
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July 23, 2008
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Demirel Lab 2008
FUNCTIONAL NANOSTRUCTURED POLYMERFUNCTIONAL NANOSTRUCTURED POLYMER--
METAL INTERFACESMETAL INTERFACES
Melik C. Demirel, PhDPearce Assistant Professor of Engineering
Materials Research Institute & Huck Life Institute of Sciences
Pennsylvania State University
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Funding �Young Investigator Award, Department of Defense
�Office of Naval Research
�Penn State University
�Institute for Complex Adaptive Matter (ICAM)
�Johnson and Johnson (USA)
�Kisco International (Japan)
�BD International (USA)
Acknowledgement
ICAM
ICAM
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Polymer / Boeing
Polymers are needed in
energy, sustainability,
clean water, health care,
informatics, defense
and security.
Boeing 787:
This new plane is 50%
by weight and 80% by
volume polymer-based
compositeBoeing 787
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Nanofiber Polymers
J. A. Matthews, et al.
Biomacromolecules 2002, 3, 232 –
238.
ELECTROSPINNINGELECTROSPINNING
M. Steinhart,et al., Adv.
Mater. 2003, 15, 706.
TEMPLATE BASED WETTING
rotate
OBLIQUE ANGLE
POLYMERIZATION
Bottom-up Top-Down
Demirel et al, Langmuir,
2007
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Similar Architectures in Nature
Cicada orni wings
Gecko footpad
Structured Structured
PolymersPolymers
100100--200nm structures with high aspect ratio (micron scale length)200nm structures with high aspect ratio (micron scale length)
Duck FeatherButterfly wings
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OBJECTIVE
We are creating nanostructured polymers with controlled physicochemical properties, such as mechanical properties, structure (morphology) and chemistry for applications in the area of nanostructured surface coatings
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TECHNICAL APPROACH
Our method is a bottom-up process based on oblique angle polymerization developed by our group.
In this process, monomer vapors produced by pyrolysis of chemically functionalized precurcors are directed at an oblique angle towards a surface to initiate structured polymer growth.
Radical
Monomer
Radical
Monomer
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Metallic, ceramic, and organic nanostructured films
Helical Si helical Au helical Alq3 parylene-PPX
Lu, RPI Zhao, U. Georgia Brett, U. Alberta Demirel, Penn State
Short history of oblique angle deposition
Kundt 1876—first columnar film
Hansma 1950—first study of morphology
Messier, Lu, Brett ~1990—metallic / ceramic films
Demirel 2005—polymeric films
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Parylene (PPX) deposition
Gorham
1960
Gorham WF.
J Polym Sci Part A-
1, 4(1966), 3027.
Demirel
2007
Langmuir, 23
(11), 5861 -
5863, 2007
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Polymer composition doesn’t change
Structured Film
Planar Film
Demirel, M.C., et al. Langmuir, 23 (11), 5861 -5863, 2007
Structured Film
FTIR TGA
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10 100 1000 10000
100
PPX-Cl
PPX-COCF3
PPX-Br
Column diameter (nm)
Column height (nm)
2000 3000 4000 500050
100
150
200
250
300
Column diameter (nm)
Column height (nm)
Evolution and GrowthScaling: d ~ hp
PPX-C ----- p= 0.12
PPX-Br ----- p= 0.17
PPX-COCF3 ---- p= 0.20
n
ClCl
n
F3C
O
0
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Growth Model
Roughness is destabilized due to oblique angle
Cetinkaya, M., Malvadkar, N., Demirel, M.C., JOURNAL OF POLYMER
SCIENCE PART B: POLYMER PHYSICS, Vol. 46, pg 640-648, 2008.
Ballistic Monte Carlo Method
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Chemistry: Polyimide and PPV
deposition
4,4'-DIAMINODIPHENYL ETHER
PYROMELLITIC DIANHYDRIDE
Co-polymerization (300 ºC,
0.1 Torr) at oblique angle
Polyimide
poly(phenylene vinylene) (PPV)
Polymerization (60 ºC, 0.1
Torr) at oblique angle
PPV
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Demirel Lab 2008Demirel, M.C., et al. Langmuir, 23 (11), 5861 -5863, 2007
Morphology Control
0
500
1000
1500
2000
2500
0 100 200 300 400 500 600 700
Series1
Series2D
A
Porosity is measured by
BET/QCM
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DC
BA
Controlling: Topology
Si Substrate PDMS Substrate
After
deposition
Before
deposition
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Functional Polymer-Metal Interfaces OBLIQUE ANGLE POLYMERIZED
FILMS
(developed by Prof. Demirel)
1. Liquid Phase Electroless
Metallization2. Vapor Phase Metallization
Applications: Catalyst, nanoparticleassembly, Biosensors, thermal
barriers, neural interfaces
Parameters
• Surface crystal structure• Surface area• Ligand and colloid binding
Parameters• Confinement• Surface crystallinity
Ions →metal nano-clusters Vapor →metal nano-clusters
Surface enhancement: increasing surface area,
introducing porosity, controlled dispersity
Controlled chemical and physical properties:
different monomer chemistry, different film
morphology.
Industrial scale production: relatively
inexpensive, no clean rooms, no lithography or
masks.
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Liquid Phase: Metal Membranes
Demirel, et al. Advanced Materials, 2007
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c
Reduction to Practice
D
500 nm
250 nm
500 nm
0 nm
C
15 µµµµm
Parylene
(helical nanostructure)
Electroless NiParylene
Ni
1 µµµµm
E
Pore
Pore
Ni
Nanostructured parylene films after Ni metallization: (C) SEM (cross-section); (D) AFM (Ni
film top); (E) SEM (Ni film top). Film regions shown in parts (A) and (B) are not the same
as those shown in parts (C), (D), and (E).
Nanostructured parylene films before metallization: (A) SEM (cross-section); (B) AFM (film top)
B
1000 nm
2000 nm
0 nm
500 nm10 µµµµm
A
Parylene
(helical nanostructure)
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Porous
Nickel
Top surface
(SEM)
EDX spectra
Cross Section
(FIB)
Characterization
Demirel, et al. Advanced Materials, 2007
3030--50nm thin porous membrane metal50nm thin porous membrane metal
Selective, covalent binding of Sn-free
Pd(II) nanoparticles at the adsorbed
ligand sites on the nanostructured PPX
surface.
Treatment of the Pd(II)-catalyzed
surface with an electroless Ni bath,
leading to reduction of Pd(II) to Pd(0)
and catalysis of electroless Ni
deposition templated by the
nanostructured PPX surface.
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Functional Polymer-Metal InterfacesOBLIQUE ANGLE POLYMERIZED
FILMS
(developed by Prof. Demirel)
1. Liquid Phase Electroless
Metallization2. Vapor Phase Metallization
Applications: Catalyst, nanoparticleassembly, Biosensors, thermal
barriers, neural interfaces
Parameters
• Surface crystal structure• Surface area• Ligand and colloid binding
Parameters• Confinement• Surface crystallinity
Ions →metal nano-clusters Vapor →metal nano-clusters
Surface enhancement: increasing surface area,
introducing porosity, controlled dispersity
Controlled chemical and physical properties:
different monomer chemistry, different film
morphology.
Industrial scale production: relatively
inexpensive, no clean rooms, no lithography or
masks.
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Vapor Phase: Metal Membranes
Au, Ag, Co, Cu, etc…
metalized
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Vapor Phase: Metal Membranes
AFM SEM
248.0748.72 cm2Deposit Ag
on top
391.9676.98 cm2Only polymer
film
Multiple of
electrode area
(0.1964cm2)
Surface areaSample
QCM /
BET
Results
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Why do we need these type of
nanostructured polymer surfaces?
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Applications
• Mechanical Properties
• Self cleaning
• Biosensor
• Energy / Catalyst
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Microtribology of Nanostructured
Materials
N
Do material anisotropies
influence friction, deformation
processes?
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Tribology of Nanostructured
Materials
- Films of Molecules or FibersFriction Anisotropy Collective Buckling
Sliding direction
Liley et al., Science 280 (1998) 273-275
Thiolipid monolayer on mica
Cao et al., Science 310 (2005) 1307
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Microtribometry Protocol
•17 ± 4 μm Conospherical
Diamond Tip
•8 μm Wear Track
•40 Sliding Cycles
Increasing Load TestConstant Load Test
Load and displacement profiles
• 100 μN Constant Load
• 300 μN Ramped LoadK. Wahl, E. So, M. Demirel
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Contact Depths During Sliding
300
250
200
150
100
50
0
-4 -3 -2 -1 0 1 2 3 4
Test 118, 100 uN load, 0-degree orientation
Lateral Position (um)Depth (nm)
Against columns
With columns
Sliding Direction
300
250
200
150
100
50
0
-4 -3 -2 -1 0 1 2 3 4
Test 118, 100 uN load, 0-degree orientation
Lateral Position (um)Depth (nm)
Against columnsAgainst columns
With columnsWith columns
Sliding Direction
300
250
200
150
100
50
0
-4 -3 -2 -1 0 1 2 3 4
Test 122, 100 uN load, 180-degree orientation
Lateral Position (um)
Depth (nm) Sliding Direction
Against columns
With columns
300
250
200
150
100
50
0
-4 -3 -2 -1 0 1 2 3 4
Test 122, 100 uN load, 180-degree orientation
Lateral Position (um)
Depth (nm) Sliding Direction
Against columnsAgainst columns
With columnsWith columns
Parallel Sliding
0°
180°
Anisotropy? YES
Tip penetrates
deeper into film
when sliding with
column tilt
Arrows indicate the
sliding direction
K. Wahl, E. So, M. Demirel
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Depth Response w/ Load
800
700
600
500
400
300
200
100
0
-6 -4 -2 0 2 4 6
Pre-scan Post-scan
Increasing Load
Lateral Displacement (um)
Depth (nm)
With Columns
Against Columns
800
700
600
500
400
300
200
100
0-6 -4 -2 0 2 4 6
Increasing Load
Lateral Displacement (um)
Depth (nm)
Pre-scan
Post-scan
Perpendicular to Columns
Depth anisotropy observed for all ordered
films over a wide range of conditions
K. Wahl, E. So, M. Demirel
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Penetration Depth vs. Load
Highly confident statistics demonstrating
depth anisotropy
K. Wahl, E. So, M. Demirel
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Mechanical Deformation Hysteresis
H
?b
∑= xb FEd
H4
3
3
64
πδ
Beam Equation
ω=÷÷
∂∂
∂∂
2
2
2
2
x
uEI
x
Solution
?c
Hooke’s Law
L
LE
A
F ∆=
∑= yc FEd
H2
4
πδ
Solution
+=+= ∑∑ )sin()cos(
3
164)sin()cos(
2
2
2αα
παδαδ
yxcb FFd
H
Ed
HDepth
Sliding perpendicular to film results in no hysteresis, predicted depths between with/against
• Variations in total penetration depth may be more strongly
correlated to film density, modulus
• Model does not include density, inter-column contact or
friction
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Applications
• Mechanical Properties
• Self cleaning
• Biosensor
• Energy / Catalyst
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Wetting Behavior
Young’s Model
Cassie’s Model
Wenzel’s Mode
Transition Model
+ Gecko State ??? (adhesive + hydrophobic) J. Liang, et al., Adv. Mat, 2007
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Adhesive and
Hydrophobic
Non-
Adhesive and
Hydrophobic
Roll off angle
< 5 degrees
Boduroglu et al, Langmuir, 2007
A B
C D
Surface Wetting
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Possible explanation!!!
0
0.5
1
1.5
2
2.5
3
3.5
4
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
r 2̂ r 3̂
Gravity ~ mg ~ Vg ~ r^3
Capillary ~ Surface Area ~ r^2
Force Balance
Note: Water drop is stable up to 40 microliter.
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Applications
• Mechanical Properties
• Self cleaning
• Biosensor
• Energy / Catalyst
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The Biosensor TreeBIOSENSORS
Electrochemical Optical Mechanical
AMporemetirc Potentiometric Impedimetric Vibrational LuminescenceIntegrated
Optics
Surface Aqustic
Wave
(SAW)
Quartz Crystal
Microbalance
(QCM)
IR
Raman
Fluorescence
Chemi-
fluorescence
SPR
Interferometer
T. Cass, C. Toumazou, Biosensors and Biomarkers, Foresight Project Review
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Raman for Biological Detection
ADVANTAGES
• Reagentless method: No reagent but provides chemical structure information (specificity)
• Single Cell Detection: No amplification of DNA (PRC) or Laboratory growth techniques.
• Applications includes identification of characteristic spectra from viruses, bacteria, or protozoa for biomedical, homeland security (CBW agents), aerospace (aerosols) areas.
• Substrate Preparation: High-throughput technique (advantage of vapor deposition), relatively inexpensive
PITFALLS
• Requires creation of database for infectious agents (Raman database)
• Requires bioinformatics tools for analyzing the database (deconvolution and pattern detection)
E.Coli
B.Cere
us
Demirel et al, Adv. Materials, 2008,
in press
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Raman v.s. SERS
Escherichia coli Raman spectrum and the SERS spectrum
Kneipp, Acc. Chem. Res. 2006, 39, 443-450
--Raman, 1920 (Nobel Prize--1930)
--SERS (1977), Van Duyne and Jeanmaire and, independently, Albrecht and Creighton
HOT-SPOTS
SERS phenomena of silver
nanoparticles
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SERS: Viral and Bacterial Detection
Representative SERS spectra of a) Adenovirus,
b)Rhinovirus, c) HIV Zhao, Nano Lett., Vol. 6, No.
11, 2006
Representative SERS spectra of Gram-negative species: a) E.
coli; b) S. Tennessee; c) K. pneumoniae; d) E. aerogenes;, e) P.
mirabilis; f) P. aeruginosa.
T. Pineda, M.S. Thesis, University of Puerto Rico, 2006
Representative SERS spectra of Gram-positive species: a)B.
subtilis; b) B. cereus; c) B. thuringiensis; d) S. epidermidis; and
e) S. aureus.
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SERS: Strain Identification
Rosch et al. , Analytical Chemistry, Vol. 78, No. 7, April 1, 2006
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SERS Substrates
• Several methods have been implemented for microorganism detection using SERS such as gold nanoparticle coated SiO2, electrochemically roughened metal surfaces, and colloidal metal particles.
Lu.J et.al. Nanotechnology 17 (2006) 5792–5797
Shanmukh et. al. Nano Letters 2006,
6, 2630.
He H. et. al. Langmuir 16,
3846-3851 (2000).
Gunnarsson, L. et al. Applied Physics Letters 78, 802-804
(2001).
Dick. L et. al. J. Phys. Chem. B 2002, 106, 853-860
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SERS DetectionThe lack of reproducibility of these techniques and uniform signal
detection make it difficult to get consistent SERS results.
Example: Influence
of gold nanoparticle
size on SERS
spectrum of
B.megaterium.
Culha et al., Journal of
Biomedical Optics 125,
054015
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Metal layer (Ag, Au)
Infectious agent Raman Laser
Single cell
Nano SERS substrate
0
500
1000
1500
2000
600800
10001200
14001600
18002000
5
10
15
20
Counts
Wave number (cm -1)
Data set
Database
Non-lithography based Polymer/Metal
SERS substrate
Demirel et al, Advanced Materials, in press, 2008
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SERS: Metal Layer Thickness
500 1000 1500 2000
0
10000
20000
30000
40000
50000
1592
1491
1157
1076
817624
SERS, t=60nm
SERS, t=90nm
Raman, BulkCount [a.u.]
Raman Shift (cm-1)
Demirel et al, Advanced Materials, in press, 2008
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SERS: Laser Wavelength
Wave number (cm-1)
500 1000 1500 2000 2500 3000
Counts
Neat FBT by 633nm laser
Au substrate by 633nm laser
Ag substrate by 633nm laser
Ag substrate by 514nm laser
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Roughness control over 2 length scale
100 1000
1
10
100
RMS roughness (nm)
film thickness (nm)
E.F. :1x105
SERS Uniformity: %99
E.F.: 2x105
SERS Uniformity: %93
Demirel et al, Advanced Materials, in press, 2008
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SERS: Life time measurement
.
Not
Measured
1138083437Ag
2369Not
measured
4612Au
After two
months
After one
month
Fresh
sample
Enhancement factor for SERS substrate
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500 1000 1500 2000
600
800
1000
1200
1400
1600
652.50164
724.3908
958.02601
1090.50001
1241.86638
1330.54659
1372.10302
1456.17654
1547.12549
1593.40894
1710.14357
E. Coli
Counts
Raman Shift (cm-1)
500 1000 1500 2000
0
2000
4000
6000
8000
1649.88
1611.121594.3
1559.63
1513.97
1477.01
1332.4
1236.22
1096.28
1078.93
1021.69
937.321
720.308
655.602
237.985
B . Cereus
Counts
R am an Sh ift (cm-1)
Fingerprint of Bacterial Samples: Single Cell
Demirel et al, Advanced Materials, in press, 2008
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400 600 800 1000 1200 1400 1600 1800 2000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
Norm
alized C
ount
Raman Shift (cm-1)
E.Coli SERS spectra collected from
25 individual cells
Reproducible Data: The peak at the 1372 cm-1 shows a relative deviation of 15%.
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What is next: Detection of Viruses
Human respiratory syncytial virus (RSV)
Patterned SERS Substrate
(PPX-Au)
500 600 700 800 900 1000 1100 1200 1300 1400 1500
Raman shift / cm-1
0
500
1000
1500
Counts
521.464
889.242 954.426
986.1521003.08
1099.48
1208.51
1226.34
1392.07
1517.19
SERS Spectra of RSV
Cryo-negative stain images recorded at a
magnification of x30,000
MacLennan, J. Virol. 2007;81:9519-9524.
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Applications
• Mechanical Properties
• Self cleaning
• Biosensor
• Energy / Catalyst
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Catalysts activity of Polymer/ Metal
surfaces: Cobalt for Hydrogen ReleaseNaBH4 + 2H2O -> 4H2 + NaBO2
pH = 12
Catalyst NaBH4 concentration (wt. %)
NaOH concentration (wt. %)
Hydrogen release rate (mL/min-g)
Reference
A-26 (Ru based) 20 10 4032 {Amendola, 2000 #12}
IRA-400 (Ru based) 12.5 1 ~9600 {Amendola, 2000 #11}
Pt/C 10 5 23,090 {Wu, 2004 #61}
Co-B 2 5 ~3500 {Wu, 2005 #21}
Pt-LiCoO2 5 5 ~24000 {Krishnan, 2005 #58}
Ru-C 10 10 6250 {Dong, 2003 #62}
Co-B 25 3 ~7500 {Lee, 2007 #18}
Co-PPXC 2.5 10 ~1500-7000 This work
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Cobalt Substrate Preparation
A B
0 20 40 60 80 100 120
0
20
40
60
80
100
Co. Wt [%
]
Co. Bath Time [min]
C
0 20 40 60 80 100 120
30
60
90
Surface Roughness [nm]
Cobalt Bath Time [min]
D
Malvadkar N., Park, S., Macdonald, M., Wang, H., Demirel, M.C.,
JOURNAL of POWER SOURCES, in press, 2008.
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Cobalt Catalyst Results
0 50 100 150 200 250
0.0
0.1
0.2
0.3
0.4 Nanostructured PPX-Co
Planar PPX-Co
Hydrogen Release Rate [ml/(m
in*cm
2)]
Cobalth Bath Time [min]
0 5 10 15 20 25
0.0
0.1
0.2
0.3
0.4
0.5
Cobalt 100 min
Hydrogen R
elease Rate [mg/(min*cm
2)]
NaBH4 Concentration [%]
11.5 12.0 12.5 13.0 13.5
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
Cobalt 100 min
Hydrogen R
elease R
ate [ml/(m
in*cm
2)]
pH value
Hydrogen formation from
Sodiumborohydride (Cobalt as
a catalyst)
NaBH4 + 2H2O -> 4H2 + NaBO2pH = 12
Concentration and
pH dependence
Malvadkar N., Park, S., Macdonald, M., Wang, H., Demirel,
M.C., JOURNAL of POWER SOURCES, in press, 2008.
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Conclusions1. Structured polymers are grown, for the first time, by an
oblique angle polymerization method. Structured Polymer growth obeys a scaling law and the growth can be modeled with a ballistic Monte Carlo method.
2. Structured Polymers offer the possibility of fabricating surfaces exhibiting tunable physical properties (i.e. modulus, hydrophobicity, toughness, porosity, etc..) by systematically varying and controlling the chemistry, morphology, and topology at the same time.
3. Structured Polymer technology is a simple and inexpensive method for the functionalization of surfaces for industrial scale applications. Applications for structured polymers: Biomedical coatings, Self Decontaminating Surfaces, Biosensors, Catalyst supports, sensor platform, Enzyme Stability, etc…
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Demirel Lab.
Demirel Lab:
•Post-doctoral Fellows: Dr. Serhan
Boduroglu, Dr. Hui Wang
•Graduate Students: Eric So, Ping Kao,
Niranjan Malvadkar, Murat Cetinkaya, Rama
Gullapalli, Sunyoung Park
•Undergraduates: Ashlee Mangan, Tomas
Marko, Brendon Purcell, Mike Anderson
Outside (Active Collaborators):
•Walter Dressick(NRL): Metallization
•David Allara(Penn State): SERS
•Kathy Wahl (NRL): Mechanical Properties
•Mary Poss (Penn State): Infectious Diseases
http://www.personal.psu.edu/mcd18/
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Thank you
More information and technical documents
are available at our group web site:
http://www.personal.psu.edu/mcd18/