Nanomaterials for space exploration applications
NanoMaterials GroupNASA Johnson Space Center
ES4/Materials and Processes Branch
Phone: 281-244-5917E-Mail: [email protected]
https://ntrs.nasa.gov/search.jsp?R=20080030261 2018-05-07T02:06:08+00:00Z
2005 2010 2015 2020 2035
Lunar MannedCrew ExplorationVehicle
ISSComplete
Lunar Robotic
Mars Robotic
Deep Space Exploration
Mars Manned
NASA’s Strategic Vision
Technology Readiness Levels (TRL)
Nanomaterials: Fundamentals to Applications
Growth/ProductionLaser and HiPco Production and
Diagnostics
CharacterizationPurity, Dispersion, Consistency, Type
SWCNT Load TransferSingle Fiber Diffusivity
ProcessingPurification
FunctionalizationDispersionAlignment
CollaborationAcademia, Industry, Government
C60DC60=10.18ÅDFe=2.52ÅDCo=2.50ÅDNi=2.50ÅDC=1.54Å
Size Comparison –C60 , Nanotubes, and Atoms
C60
Single WallCarbon Nanotube
C60DC60=10.18ÅDFe=2.52ÅDCo=2.50ÅDNi=2.50ÅDC=1.54Å
Size Comparison –C60 , Nanotubes, and Atoms
C60
Single WallCarbon Nanotube
Unique Properties• Exceptional strength• Interesting electrical properties
(metallic, semi-conducting, semi-metal)• High thermal conductivity• Large aspect ratios• Large surface areas
Possible Applications• High-strength, light-weight fibers and
composites• Nano-electronics, sensors, and field
emission displays• Radiation shielding and monitoring• Fuel cells, energy storage,
capacitors • Biotechnology• Advanced life support materials• Electromagnetic shielding and
electrostatic discharge materials• Multifunctional materials• Thermal management materials
Current Limitations• High cost for bulk production• Inability to produce high quality, pure, type
specific SWCNTs• Variations in material from batch to batch• Growth mechanisms not thoroughly
understood• Characterization tools, techniques and
protocols not well developed
Nanomaterials: Single Wall Carbon Nanotubes
Growth, Modeling, Diagnostics and Production
Modeling, Diagnostics, and Parametric Studies
Objective: Ensure a reliable source of single wall carbon nanotubes with tailored properties (length, diameter, purity, chirality)
NASA / Rice University2nd Single-Wall Nanotube Growth Mechanisms Workshop
April 2005Guadalupe River Ranch, Texas
Growth, Modeling, Diagnostics and Production
Characterization: Purity, Dispersion & Consistency
Standard Nanotube Characterization Protocol
Arepalli, et al., Carbon, 2004
8000 10000 120000.0
0.2
0.4
0.0
0.1
(a)
REFERENCE (R2)
A(T,R2)
= 0.141A(T,R2)A(S22,R2)
A(S22,R2)
R2
Abs
orba
nce
Wavenumber (cm-1)
New Purity Reference Standard
Haddon, 2003
TPO
0 200 400 600 800 10000.0
0.1
0.2
0.3
5%, 763 oC
17%, 633 oC
5%, 527 oC
37%, 454 oC
14%, 382 oC
xc1�382.47879� ±16.
w1�228.23241� ±14.
A1�13.93993� ±1.99063
xc2�454.29423� ±0.2
w2�102.48077� ±0.9
A2�36.93765� ±1.24083
xc3�527.24674� ±0.1
w3�34.67277� ±0.31586
A3�5.04174� ±0.08191
xc4�633.01953� ±2.0
w4�138.11402� ±4.2
A4�16.7643� ±0.92689
xc5�763.38627� ±1.5
w5�88.42463� ±1.96689
A5�4.57328� ±0.28528
DT
G, %
/o C
T, oC
0 200 400 600 800 10000.0
0.1
0.2
0.3
5%, 763 oC
17%, 633 oC
5%, 527 oC
37%, 454 oC
14%, 382 oC
xc1�382.47879� ±16.
w1�228.23241� ±14.
A1�13.93993� ±1.99063
xc2�454.29423� ±0.2
w2�102.48077� ±0.9
A2�36.93765� ±1.24083
xc3�527.24674� ±0.1
w3�34.67277� ±0.31586
A3�5.04174� ±0.08191
xc4�633.01953� ±2.0
w4�138.11402� ±4.2
A4�16.7643� ±0.92689
xc5�763.38627� ±1.5
w5�88.42463� ±1.96689
A5�4.57328� ±0.28528
DT
G, %
/o C
T, oC
NASA/NIST2nd Characterization
WorkshopJanuary 2005
Gaithersburg, MD
Applications for Human Space Exploration
Power / Energy Storage Materials
– Proton Exchange Membrane (PEM) Fuel Cells– Supercapacitors / batteries
Advanced Life Support– Regenerable CO2 Removal– Water recovery
Thermal Management and Protection
– Ceramic nanofibers for advanced reentry materials– Passive / active thermal management (spacesuit fabric, avionics)
Electromagnetic / Radiation Shielding and Monitoring
– ESD/EMI coatings– Radiation monitoring
Multi-functional / Structural Materials
– Primary structure (airframe)– Inflatables
Nano-Biotechnology– Health monitoring (assays)– Countermeasures
Electrical Power / Energy Storage Systems
ShuttleShuttle3x Alkaline Fuel Cells
ISS ISS Photovoltaics & NiHPhotovoltaics & NiH2 2
batteriesbatteries
NiMH, LiNiMH, Li--MnOMnO2 2 and Ag/Znand Ag/Znbatteriesbatteries
Specific Power (W/kg)
Spec
ific
Ener
gy(W
h/kg
)
10
102
102 103 104
103
104
10
Fuel Cell
Battery Supercapacitor
Specific Power (W/kg)
Spec
ific
Ener
gy(W
h/kg
)
10
102
102 103 104
103
104
10
Fuel Cell
Battery Supercapacitor
Spec
ific
Ener
gy(W
h/kg
)
10
102
102 103 104
103
104
10
Fuel Cell
Battery Supercapacitor
Advanced Power Generation: Hybrid Systems
• Pulse power source• Fast charge/discharge• Very high power density• Virtually unlimited cycle life
SupercapacitorBatteryFuel Cell
+ +
• Continuous energy supply• High energy density• Low power density
• Smaller, lighter, longer life with hybrid
• Intermediate power density• Intermediate energy density
Energy-powertradeoff
Advanced PEM Fuel Cells – Nanotube Electrodes
• Carbon nanotube electrode assemblies for proton exchange membrane (PEM) fuel cells
• Membrane Electrode Assembly (MEA) formed from a NafionTM
membrane sandwiched between nanotube electrodes with Pt catalyst
• Increased surface area of the electrodes•Enhanced thermal management •Reduce Ohmic losses – increase efficiency• Higher power density• Small diameter HiPco tubes may enhance H2dissociation – optimized porosity•More uniform current density
Source: www.eere.energy.gov
Advanced PEM Fuel Cells - Characterization
Characteristic Technique/ Instrument Destructive When Results Characteristic Technique/
Instrument Destructive When Results
Amount of Pt, Fe, Co, Ni X Ray Photoelectron/Fluorescence Spectroscopy
no After BP is baked (Part
5);
Quan Mass Scale no After BP is (1) made and (2) baked (Part 3 and Part 5)
Quan
Platinum Dispersion Scanning Electron Microscopy (SEM)
yes After BP is baked (Part
5)
Qual Thickness Randall&Stickney Dial Gauge
no After BP is (1) made and (2) baked (Part 3 and Part 5)
Quan
Platinum Dispersion Transmission Electron Microscopy (TEM)
yes After BP is baked (Part
5)
Qual Interface and Thickness Freeze Fracture then SEM
yes After MEA is made (Part 7)
Qual/Quan
Electrical Conductivity Probe Meter no After MEA is made (Part
7)
Qual Interface Flash IR Thermography
no After MEA is made (Part 7)
Qual
Surface Area & Porosity Brunauer, Emmett, and Teller Analysis (BET)
yes After BP is (1) made and (2)
baked (Part 4 and Part
5)
Quan Interface Current Voltage Curve
no During Fuel Cell Testing
Quan
Advanced PEM Fuel Cells - Characterization
Prototype Membrane Electrode AssemblyCarbon FiberGas Diffusion Layer (GDL)
Single Wall Carbon Nanotube (SWCNT) Electrode
NafionTM
Membrane
Carbon Fiber(GDL)
SWCNT Electrode
SWCNT interfacein MEA
NafionTM
interface in MEA
Characterization PEMFC: TEM of Electrodes Made with Purified SWCNTs
•EDX data does not indicate the presence of Fe (would show up at about 6.4 keV).
•EDX does indicate the presence of Pt, therefore we presume that the visible nanoparticles are composed of Pt.
•TEM shows a range of Pt particle sizes between 2nm and 10nm.
•XPS data indicates that Pt is metallic. This indicates complete decomposition of the precursor.
TEM provides particle size distribution and EDX Shows elemental composition.
Characterization PEMFC: TEM of Electrodes Ultramicrotomy
TEM Ultramicrotomy Study to characterization interface between GDL, electrodes and Nafion
PEMFCPEMFC
•• Developed Characterization protocolDeveloped Characterization protocol•• Test capability at NASA JSC Test capability at NASA JSC •• Achieving catalyst size and performanceAchieving catalyst size and performance•• Higher performance at lower current Higher performance at lower current
loading loading –– increased PEMFC kineticsincreased PEMFC kinetics
NASA JSC Nanomaterials: Environmental ApplicationsNASA JSC Nanomaterials: Environmental Applications
Water PurificationWater Purification•• NASA JSC Structural Engineering and NASA JSC Structural Engineering and Crew Crew
& Thermal Systems& Thermal Systems Divisions Divisions
••Use light induced production of singlet oxygen Use light induced production of singlet oxygen
by fullerenes to destroy harmful by fullerenes to destroy harmful
microbes in water suppliesmicrobes in water supplies
•• Developing Developing process for attaching fullerenes process for attaching fullerenes
to fiber optic cablesto fiber optic cables
•• CDDF 2005 CDDF 2005 –– Report Due December 2005Report Due December 2005
C60
Air Revitalization: COAir Revitalization: CO22 RemovalRemoval
••Remove CORemove CO22 from cabin air in order to extend the use of cabin air suppliesfrom cabin air in order to extend the use of cabin air supplies
••Only a small amount of COOnly a small amount of CO22 can contaminate a large amount of cabin aircan contaminate a large amount of cabin air
Cabin
RCRS
Lithium Hydroxide: Not suited for long duration missions since it is non regenerable
Air Revitalization: Some Current TechnologiesAir Revitalization: Some Current Technologies
Zeolite 5A: Physisorption of CO2– Requires 200C to renew the adsorbent – high power
consumption– Lower surface area to volume ratio– Non selective
MetOx – Metal Oxide (AgO) reacts with CO2 to form a carbonate. – Large system mass – not optimal for PLSS– Also requires high temperature
SecondarySecondary
TertiaryTertiary
PrimaryPrimaryCatalyzed by moistureCatalyzed by moisture
Depending on their bonding Depending on their bonding amines have varying degrees amines have varying degrees of affinity for COof affinity for CO22 capture and capture and desorptiondesorption
Primary binds COPrimary binds CO2 2 tightly, thus tightly, thus inhibiting desorption while inhibiting desorption while tertiary amines bind COtertiary amines bind CO22 poorlypoorly
Secondary amines are Secondary amines are preferred for pressure swingpreferred for pressure swing
Supported Amines for Air RevitalizationSupported Amines for Air Revitalization
NN--aminoethylpiperazineaminoethylpiperazine
The State of the Art in Amine SystemsThe State of the Art in Amine Systems
Polymer Bead and Aluminum Structure
Advanced solid amine bed system flown in mid-1990’s (pressure swing)– Volume constraints, thermally inefficient, amine volatility– Not suited for planetary use (need temperature swing) – Surface area ~100 m2/g
Need for new material: high surface area, high thermal conductivity, ability to be coated with amine system
Carbon nanotubes may offer a thermally conductive high surface area light weight support material for this application
Initial Results and Technology AssessmentInitial Results and Technology Assessment
ResultsResults•• Carbon Nanotubes have Carbon Nanotubes have
high surface area: bucky high surface area: bucky pearls, fibers, bucky pearls, fibers, bucky paperpaper
•• TGA experiment: the TGA experiment: the amine is reactive with the amine is reactive with the COCO22 gas streamgas stream
•• Poor adherence to Poor adherence to nanotube surface nanotube surface --requires a specific pore requires a specific pore size and shapesize and shape
•• We need a better way to We need a better way to integrate the support integrate the support phase with the aminephase with the amine
Materials Development and TestingMaterials Development and Testing
••Collaborations for Collaborations for functionalization of SWCNTsfunctionalization of SWCNTs
••Dr. W. E. Billups group (Rice Dr. W. E. Billups group (Rice University)University)
••Dr. J. Tour group (Rice Dr. J. Tour group (Rice University)University)
••Collaboration with Dr. T. Filburn Collaboration with Dr. T. Filburn (University of Hartford)(University of Hartford)
––Determine the types of Determine the types of amines that would be suitable amines that would be suitable for spaceflight needsfor spaceflight needs
––Testing methods for Testing methods for equilibrium adsorption and equilibrium adsorption and desorption and well as cyclic desorption and well as cyclic behaviorbehavior
Hirsch et al.
Functionalization of SWCNTs with Amine GroupsFunctionalization of SWCNTs with Amine Groups
••Since amines are volatile the coating would be prone to degradatSince amines are volatile the coating would be prone to degradation ion during repeated thermal or vacuum driven renewal of the adsorbenduring repeated thermal or vacuum driven renewal of the adsorbent. t.
••Chemically bonding of the amine to the support phase was a solutChemically bonding of the amine to the support phase was a solution to ion to this problemthis problem
Hirsch et al.
The argument for functionalizationThe argument for functionalization
•• Amenable to repeated cyclingAmenable to repeated cycling–– Materials are thermally stable up to 100 C. (Thermal Materials are thermally stable up to 100 C. (Thermal
desorption takes place at 50 desorption takes place at 50 –– 60 C)60 C)–– Chemical bonding of the amine to the support Chemical bonding of the amine to the support
ensures these materials will be amenable to repeated ensures these materials will be amenable to repeated vacuum desorptionvacuum desorption
•• We have the tools and capability to manufacture We have the tools and capability to manufacture materialsmaterials–– Collaborators at Rice (Tour and Billups) are experts in Collaborators at Rice (Tour and Billups) are experts in
the area of nanotube functionalizationthe area of nanotube functionalization–– Chemistry is repeatable and reliable.Chemistry is repeatable and reliable.–– High amine loadings are possible especially with long High amine loadings are possible especially with long
branched amine polymersbranched amine polymers
Active / Passive Thermal Management Materials
• SWNT thermal properties are extremely anisotropic; SWNT axial conductivity is comparable to that of diamond (2150 W/m-K)
• Nylon Spandex/SWNT fabric improves crew member’s thermal comfort and increases heat transfer rate to EMU sublimator (SBIR)
• Active heat acquisition and transport applications in concept stage (advanced coldplate, interface, fluids)
• New single-fiber thermal diffusivity tool developed by JSC Nano Team and ORNL
The rmal Diffus ivity
0.001
0.0015
0.002
0.0025
0.003
0.0035
0 10 20 30 40 50 60
Nanofibe r c ompos ition w t.%
Diff
usiv
ity (c
m^2
/sec
)
S e rie s 1
S e rie s 2
S e rie s 3
S e rie s 4
RTV/Tubes@rice (NASA)
PP/VGCF (Rice)ABS/Tubes@rice (Rice)
RTV/VGCF (NASA)
SWNTSWNTVGCFVGCF
The rmal Diffus ivity
0.001
0.0015
0.002
0.0025
0.003
0.0035
0 10 20 30 40 50 60
Nanofibe r c ompos ition w t.%
Diff
usiv
ity (c
m^2
/sec
)
S e rie s 1
S e rie s 2
S e rie s 3
S e rie s 4
RTV/Tubes@rice (NASA)
PP/VGCF (Rice)ABS/Tubes@rice (Rice)
RTV/VGCF (NASA)
SWNTSWNTVGCFVGCF
Matrix
Fiber
Matrix
Fiber
Nylon Spandex/SWNT Fabricfor Spacesuits
Single Fiber Thermal Diffusivity(JSC and ORNL)
ESD and EMI Materials with Nanotubes
• Application– SWNTs in a polymer at low concentrations to shield electronics from
electromagnetic interference (EMI) and for electrostatic discharge (ESD) protection of sensitive electronics components.
– Advantages – lightweight, humidity independent, flexible, ideal for coatings
Conducting Polymers from Nanotube Fillers
1.E+00
1.E+02
1.E+04
1.E+06
1.E+08
1.E+10
1.E+12
1.E+14
1.E+16
1.E+18
0 10 20 30 40 50 60 70 80
Concentration in weight %
PP/VGCF'sEpoxy/SWNT'sPP/VGCF'sPVC/ALPE/Cu
ESD range
ABS/SWNT’s EMI range
Insulating
Surf
ace
Res
istiv
ity(o
hm/s
q)
E.V. Barrera et al., Rice University
• Testing plan in work with EV (EMI)
• Industry-produced composites tested in RITF (ESD)
Carbon Nanotube Radiation Dosimeter
Compelling need to directly measure the radiation environment of spacecraft and compare to models for safety to humans for EVA and future space travel
• SWNTs respond at the particle level—radiation particle bombardment may be quantitatively detectable
• Fly initially as a passive experiment to gather real-time radiation dose on orbit
• Applicable for commercial usage by Medical, Nuclear industries
SummarySummary
• Overview of NASA JSC NanoMaterials Project– Need– NanoMaterials Growth– NanoMaterials Characterization– NanoMaterials Processing– NanoMaterials Application
• NanoMaterials for PEMFC• Presented work for developing solid-supported
amine adsorbents based on carbon nanotube materials– Materials testing– Functionalization of SWCNTs
• Briefly: Other Application areas
Nanomaterials for space exploration applications
Questions?
MicroscaleMicroscale Testing of Equilibrium COTesting of Equilibrium CO22 CaptureCapture
•• TGA/DSC experiment: Measure the weight change of a sample upon eTGA/DSC experiment: Measure the weight change of a sample upon exposure to COxposure to CO22+H+H22O stream O stream –– DSC shows heat flow indicative of amine/ CODSC shows heat flow indicative of amine/ CO2 2 reactionreaction
•• Recent upgrade: Residual gas analyzer measures the change in CORecent upgrade: Residual gas analyzer measures the change in CO22 concentration concentration
Oxygen Nitrogen
Carbon
Liang et al. 2004
Characterization of Functionalized SWCNTsCharacterization of Functionalized SWCNTs
XPS Spectrum of LXPS Spectrum of L--PEI functionalized SWCNTSPEI functionalized SWCNTS
TGA for PEI functionalized SWCNTSTGA for PEI functionalized SWCNTS
Raman Spectrum (780 nm) of:Raman Spectrum (780 nm) of:a) Purified SWCNTS b) Dodecylated SWCNTS as synthesized c) Dodeca) Purified SWCNTS b) Dodecylated SWCNTS as synthesized c) Dodecylated SWCNTS after heating ylated SWCNTS after heating –– the groups have been removedthe groups have been removed
1300
1350
1400
1450
1500
1550
1600
1650
1700
1750
1800
392 394 396 398 400 402 404 406
Binding Energy (eV)
Cou
nts
T = 200
T = 400
T = 600
TGA/XPS Study of the Thermal Stability of Functionalized TGA/XPS Study of the Thermal Stability of Functionalized SWCNTsSWCNTs
AnilineAnilineXPS Data Spectra at 200C,400C and 600CXPS Data Spectra at 200C,400C and 600C
TGA Weight LossTGA Weight Loss
TGA/XPS study of removal of functional groupsTGA/XPS study of removal of functional groups
••Heat samples to various temperature and observe Heat samples to various temperature and observe weight lossweight loss
••Examine XPS peaks characteristic of groups of Examine XPS peaks characteristic of groups of interestinterest
••Correlate weight loss to loss of functional groupCorrelate weight loss to loss of functional group
Active / Passive Thermal Management Materials for Space• SWNT thermal properties are extremely anisotropic; SWNT axial conductivity is comparable to that of diamond (2150 W/m-K)
• Nylon Spandex/SWNT fabric improves crew member’s thermal comfort and increases heat transfer rate to EMU sublimator (SBIR)
• Active heat acquisition and transport applications in concept stage (advanced coldplate, interface, fluids)
• New single-fiber thermal diffusivity tool developed by JSC Nano Team and ORNL
The rmal Diffus ivity
0.001
0.0015
0.002
0.0025
0.003
0.0035
0 10 20 30 40 50 60
Nanofibe r c ompos ition w t.%
Diff
usiv
ity (c
m^2
/sec
)
S e rie s 1
S e rie s 2
S e rie s 3
S e rie s 4
RTV/Tubes@rice (NASA)
PP/VGCF (Rice)ABS/Tubes@rice (Rice)
RTV/VGCF (NASA)
SWNTSWNTVGCFVGCF
The rmal Diffus ivity
0.001
0.0015
0.002
0.0025
0.003
0.0035
0 10 20 30 40 50 60
Nanofibe r c ompos ition w t.%
Diff
usiv
ity (c
m^2
/sec
)
S e rie s 1
S e rie s 2
S e rie s 3
S e rie s 4
RTV/Tubes@rice (NASA)
PP/VGCF (Rice)ABS/Tubes@rice (Rice)
RTV/VGCF (NASA)
SWNTSWNTVGCFVGCF
Matrix
Fiber
Matrix
Fiber
Nylon Spandex/SWNT Fabricfor Spacesuits
Heat AcquisitionHeat Transport
Single Fiber Thermal Diffusivity(JSC and ORNL)
ESD and EMI Materials with Nanotubes• Application
– SWNTs in a polymer at low concentrations to shield electronics from electromagnetic interference (EMI) and for electrostatic discharge (ESD) protection of sensitive electronics components.
– Advantages – lightweight, humidity independent, flexible, ideal for coatings
Conducting Polymers from Nanotube Fillers
1.E+00
1.E+02
1.E+04
1.E+06
1.E+08
1.E+10
1.E+12
1.E+14
1.E+16
1.E+18
0 10 20 30 40 50 60 70 80
Concentration in weight %
PP/VGCF'sEpoxy/SWNT'sPP/VGCF'sPVC/ALPE/Cu
ESD range
ABS/SWNT’s EMI range
Insulating
Surf
ace
Res
istiv
ity(o
hm/s
q)
E.V. Barrera et al., Rice University
• Testing plan in work with EV (EMI)
• Industry-produced composites tested in RITF (ESD)
Nanoshells for Thermal Control Coatings
Courtesy of NanoSpectra
• Nanoshells offer possibility of designing thermal control coatings
• Thermo-optical properties manipulated by nanoshell geometry
– ratio of silica core to shell thickness
– independent of overall organization of nanoshells
• Interested in nanoshell design with low solar absorbtivity and high emittanceTMJ Paint with Varying Nanoshell Concentrations
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
250 750 1250 1750 2250 2750Wavelength (nm)
Ref
lect
ance
AJ - 0.067 mg/mlAG - 0.2 mg/mlAD - 0.6 mg/mlAB - 1.8 mg/mlTMJ
Carbon Nanotube DosimeterCompelling need to directly measure the radiation environment of spacecraft and compare to models for safety to humans for ISS and future space travel
• SWNTs respond at the particle level—radiation particle bombardment may be quantitatively detectable
• Fly initially as a passive experiment to gather real-time radiation dose on orbit
• Applicable for commercial usage by Medical, Nuclear industries
Nanotechnology & Human SpaceflightKey Enabler to Human & Robotic Exploration
Current Nanoscale R&D on Human Spaceflight Applications- Electromagnetic Shielding Materials- Proton Exchange Membrane – PEM - Fuel Cells - Nanotube-Based Structural Composites- RCRS - Regenerable CO2 Removal System- Ceramic Nanofibers for Thermal Protection Materials- High Thermal Conductivity Fabric for Spacesuits- Radiation Resistance/Protection- Passive Radiation Dosimeter- Active Thermal Control Systems for Space- Nanoshells for Thermal Control Coatings
Technology Needs for Long-Duration Human Spaceflight- Reduced mass / volume- Greater reliability of materials/systems- System health monitoring & repair- Air revitalization- Water recovery- Human health diagnosis & treatment- Radiation protection & detection- In-space manufacturing
Human Spaceflight applications will drive unique advances in…- Safety and Toxicology- Reliability and Durability
Nano-Engineered Materials- Truly multi-functional materials- Best known mechanical, thermal, and electrical properties exist now at the nanoscale- Highest possible surface area
