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Insulation Chemistry on Earth and Beyond: Polyimide and Polyamide Aerogels
Mary Ann Meador Senior Scientist, NASA Glenn Research Center
Paulomi Majumder Managing Editor, ACS Macro Letters, Biomacromolecules, Macromolecules and ACS Biomaterials Science & Engineering
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National Aeronautics and Space Administration
Insulation Chemistry on Earth and Beyond: Polyimide and Polyamide Aerogels
Mary Ann Meador NASA Glenn Research Center Cleveland, OH www.nasa.gov
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National Aeronautics and Space Administration
What are aerogels?
Sol
Gel
• Highly porous solids made by drying a wet gel without shrinking • Pore sizes extremely small (typically 10-40 nm)—very good insulation • 2-4 times better insulator than fiberglass under ambient pressure • 10-15 times better in light vacuum • Invented in 1930’s by Prof. Samuel Kistler of the College of the Pacific
Aerogel
Typical monolithic silica aerogels
www.nasa.gov
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National Aeronautics and Space Administration
Current aerogel products and market BASF Slentite panels Aerogel Technologies Airloy Cabot Lumira Aerogel in skylights Grand Rapids, Mi
Aspen Aerogels Pyrogel pipe insulation
Main players—silica aerogels
Blueshift AeroZero
Emerging players
www.nasa.gov
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National Aeronautics and Space Administration
Comparison of Aspen Aerogels blanket insulation with traditional insulation -200
Temperature (°F) 200 400 600
0
800
1.6
1000
1200 250
Mineral Wool Pipe & Board
1.4 Mineral Wool Blanket
1.2
150
1.0 0.8 0.6 0.4
0.2
Calsil
100
Perlite Cellular Polystyrene glass Cryogel Z
Pyrogel XT
PUR/PIR Spaceloft
0.0 -200
-100
0
100
200
200
50
Thermal Conductivity (mW/m-K)
Thermal Conductivity (Btu-in/hr-ft2-°F)
-400
0 300
400
500
600
Temperature (°C)
Source: George Gould, Aspen Aerogels www.nasa.gov
Audience Survey Queson market is worth about $44 billion. About what percentage of that is currently aerogel?
• 0.01 percent • 1 percent • 10 percent • 30 percent
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Audience Survey Queson market is worth about $44 billion. About what percentage of that is currently aerogel?
• 0.01 percent • 1 percent • 10 percent • 30 percent
* Though aerogels are superior insulation, most current products are silica based which are limited to particulate or composite, which can be dusty. Emerging technologies are overcoming that but costs are still high compared to conventional insulation. 17
National Aeronautics and Space Administration
Monolithic silica aerogels out-perform particulate forms as insulation However, silica aerogels are extremely fragile…
…and therefore limited to a few exotic NASA applications
Cosmic dust collector – Stardust Program
Insulation on rovers
www.nasa.gov
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National Aeronautics and Space Administration
Potential applications for durable aerogels in aeronautics and space exploration
Cryotank Insulation
Fan engine containment (Ballistic protection)
Antenna substrates
Sandwich structures Ultra-lightweight, multifunctional structures for habitats, rovers
Propellant tanks
Heat shielding Inflatable aerodynamic decelerators
Insulation for EVA suits and habitats www.nasa.gov
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National Aeronautics and Space Administration
Durable aerogels by reinforcing silica aerogels with polymers
Native • • •
Versatile: cross-linking with variety of polymers Collaboration with Aspen Aerogels to scale up streamlined process
Polymer reinforced aerogels used to insulate cryotanks—collaboration with MSFC
•
Cross-linked
Two order of magnitude increase in strength at the same density Does not change pore structure
Low density... to higher density, same aerogel pore structure www.nasa.gov
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National Aeronautics and Space Administration
Hypersonic inflatable aerodynamic decelerator concept • Hard aeroshells used to land rovers on Mars limit size of payload • Inflatable structure overcomes this limitation • Concept shown constructed from a series of stacked inflatable tori tied with a network of straps • Flexible thermal protection system on fore body • More information about successful test launch: http://www.nasa.gov/centers/goddard/news/features/2012/IRVE3.html
www.nasa.gov
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National Aeronautics and Space Administration
Baseline insulation for HIAD was Pyrogel-2250 • Composite insulation: silica aerogel in batting • Flexible but sheds dust particles on handling • Begins to out gas at 380 oC • In high heat flux testing, time to 300 oC of bottom thermocouple related to weight of insulation LCAT Run 2340
Arm 5 -20-34 Specimen STAG-11-G • Lost % weight during test
2D Graph 2
Four layers Pyrogel 2250
220
1200 900
TC3R TC3K TC4K
600
TC5K
300
TC6K TC7K
0 0
100
200
300
Time, seconds
400
500
Nextel BF-20
200
Nextel BF-20
180
Pyrogel 2250 Pyrogel 2250 Pyrogel 2250 Pyrogel 2250 Kapton
Time to 300 oC
TC3R TC3K TC4K TC5K TC6K TC7K
o
Temperature, C
1500
160 140 120 100 80 5.5
6.0
6.5
7.0
7.5
8.0
8.5
Weight, g 4 layers Pyrogel 2250 www.nasa.gov
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National Aeronautics and Space Administration
Polyimide aerogels • Family of polymer aerogels made by crosslinking polyimide oligomers to form gel network • Supercritical fluid extraction to remove liquid from gels
Meador, US Patent 9,309,369, April 12, 2016. Meador and Guo, US Patent 9,109,088, August 18, 2015. Nguyen and Meador, US Patent 8,974,903, March 10, 2015. www.nasa.gov
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National Aeronautics and Space Administration
Typical PI Aerogel Process
Monomers mixed in NMP
Solution poured into mold
Solvent exchange into acetone
Extracted after gelation
Supercritical CO2 extraction www.nasa.gov
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National Aeronautics and Space Administration
Polyimide 3D network using T8-POSSfirst successful formulations NH2
H2N
O O H2N
O
Si
O
Si
O Si O Si
H2N
NH2 Si
O
NH2
Si O
NH2
Si O
O
O Si
O NH2
H2N
BAX
• PI cross-linked with POSS • Chemically imidized with pyridine/ acetic anhydride • BPDA-(BAX-BPDA)n; n = 10 to 25 • Low shrinkage (~10 %) • Density: ~0.1 g/cm3 • Porosity > 90 %
BPDA
BPDA
Guo, et al, ACS Appl. Mater. Interfaces, 2011, 3 (2),546-552 www.nasa.gov
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National Aeronautics and Space Administration
Cross-linked polyimide aerogels cast as thin film are flexible • Collaboration with Prof. Miko Cakmak, University of Akron • Density of film is similar to molded cylinder • Middle picture is 9” x 13” pan; film is folded multiple times • Currently can cast up to 18” inches wide, 8 ft. long
As-cast wet films
Dry aerogel www.nasa.gov
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National Aeronautics and Space Administration
Polyimide Aerogel Development NH2
H2N
O O H2N
O
Si
H2N
NH2
O Si O
O
Si
O Si O Si
H2N
NH2 Si
Si O
NH2
Moisture resistant
O
O Si
O NH2
• Two cross-linking approaches evaluated • Over thirty different combinations of backbone chemistry studied • Formulations identified with
• 100s of enquiries from companies for commercial products
2D Graph 2 40 Thermal Conductivity, mW/m-K
– Best moisture resistance – Best mechanical properties at lowest density – Low thermal conductivity – Short term stability up to 400 oC
Porous aerogel structure
35 30
Low thermal conductivity
25 20 15
BAX 760 torr BAX 0.01 torr ODA 760 torr ODA 0.01 torr
10 5 0 20
60
100
140
180
220
o
Test temperature, C
www.nasa.gov
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National Aeronautics and Space Administration
LCAT test—Saffil in LCAT Run 2428 - 04 October 2012 Arm 5 - Specimen STAG-36-2 combination withTwo PIlayers aerogel Pyrogel 2250, two layers PI2 aerogel 1500 TC2R TC3R TC4K TC5K TC6K
1200
o
Temperature, C
• Layer of Saffil • Two equivalent thicknesses PI aerogel – 50% DMBZ \ 50% ODA
900 600 300
• Test stopped after 247 s – Bottom TC reached 300 oC
0 0
100
200
300
400
500
Time, seconds Nextel BF-20
• Top of PI stack ~590 oC max TC2R
Nextel BF-20 Saffil
TC3R
• PI lost much less weight than Pyrogel
TC4K TC5K TC6K
PI aerogel PI aerogel Kapton
www.nasa.gov
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National Aeronautics and Space Administration
Multifunctional, Universal Thermal Insulation System • Current multilayer insulation (MLI) only functions in vacuum – Layers of Mylar separated by scrim layers Baseline MLI (Mylar + scrim)
• MLI incorporating aerogel in place of scrim reduces TC by 23-37% • Partnership with JSC and GRC
Pi aerogel 2D Graph 1
+ Mylar
0.030 Thermal Conductivity, W/m-K
• Aerogel is best insulation in gaseous environment
0.028
Baseline MLI (Mylar with scrim) PI aerogel + Mylar
0.026 0.024 0.022 0.020 0.018 0.016 0.014 -140 -120 -100 -80
-60
-40
-20
0
20
40
Temperature, oC
MLI with and without aerogel tested under simulated Mars atmosphere (8 Torr Argon, -120 to 20 oC) www.nasa.gov
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Audience Survey Ques
