Bauer, Brint M.

Coan, Mary R.

Devor, Robert W.

Gibson, Tracy L.

NASA Technical Reports Server

Familiarization and 
Detection of 
Green Monopropellants
Mary R. Coan PhD
Tracy L. Gibson PhD
Robert W. DeVor PhD
Brint M. Bauer
Kennedy Space Center
August 4, 2015
https://ntrs.nasa.gov/search.jsp?R=20150015582 2019-08-31T07:18:42+00:00Z
Outline
 Background
 Detection Methods
 Hydroxylammonium Nitrate (HAN) – AF-M315E
 Ammonium Dinitradmide (ADN) – LMP-103S
 Safety Considerations
 Conclusions
Background
 “Green” Monopropellants AF-M315E and LMP-103S
 Reduced Toxicity and Increased Performance compared to Hydrazines
 Hydroxylammonium Nitrate (HAN) based Monopropellant (AF-M315E)
 Developed by US Air Force Research Laboratory
 Ammonium Dinitradmide (AND) based Monopropellant (LMP-103S)
 Developed by ECAPS (Swedish Space Corporation)
 Little is known about the safety and handling of “Green” Monopropellants at 
NASA Kennedy Space Center (KSC)
 Familiarization and Detection of Green Monopropellants
 Project goals
 Evaluate detection methods for HAN- and ADN-based monopropellants
 Develop detection kits for HAN- and ADN-based monopropellants
 Become familiar with HAN/ADN properties
 Funded by NASA Kennedy Space Center Funds
Hydroxyammonium Nitrate –
HAN 
 Primary component of AF-M315E monopropellant
 42% Hydroxyammonium Nitrate (HAN)
 Negligible vapor pressure 
 Eliminates traditional monitoring techniques 
 Requires physical contact with detection method
 “Green” Monopropellant AF-M315E
 Produced by Air Force Research Laboratory (AFRL)
 Negligible vapor pressure eliminates traditional monitoring 
techniques
 NASA Technology Demonstration Mission (TDM) 
 Awarded to Ball Aerospace & Technologies Corporation 
 Green Propellant Infusion Mission (GPIM) is scheduled for 2016
 Participant in F-16 Emergency Power Unit (EPU) test conducted at 
NASA  Marshall Space Flight Center (MSFC)
AF-M315E Lot #33
Detection Methods Evaluated
 Colorimetric
 Passive method 
 Wide range of possible 
color reagents
 May be useful for 
containment/cleanup
 COTs Sensors
 Vapor Sensors
 Ammonia-based sensors 
 Actively-pumped and 
diffusion-based systems
 Liquid Detection 
 Detect Conductive Liquids
 Water and/or Chemical 
Hydrazine Dosimeter Badge
Hydrazine Vapor MonitorRLE Technologies SeaHawk
LD310 Single Zone Monitor
COTS Sensors: Liquid Detection
 RLE Technologies Chemical Sensing 
Cable
 Detects a variety of conductive chemical liquids
 Previously untested using the “Green” 
Monopropellant AF-M315E
 Chemically Resistance to several acids in 
accordance to ASTM D543
 Operating Temperature Range: -40° to 85°C
 Available in standard or custom lengths
 Constructed from thermally bonded polymer 
coated carrier
 More information can be found at 
 http://rletech.com/our-products/sensing-
cables/chemical-sensing-cable/
RLE Technologies Chemical
Sensing Cable
RLE Technologies SeaHawk
LD310 Single Zone Monitor
Liquid Detection – Test Results
 The initial RLE Technologies Chemical Sensing Cable sensor tests 
were performed using the following aqueous solutions (for baseline 
purposes): 18 MΩ water, 0.5% sodium chloride solution, 0.1 M 
ammonium hydroxide solution, and 0.1 M sodium hydroxide solution. 
 Results of this testing indicate that the RLE Chemical Sensing Cable is 
capable of detecting AF-M315E within 10 seconds of submersion, 
regardless of affected area even at a surface coverage of 1”. 
 Deionized H2O produced similar results, suggesting that the RLE Chemical Sensing 
Cable would not be useful in an environment in which moisture would be an issue, 
as this may lead to false positives. 
Submersion Test of RLE Chemical Sensing 
Cable, AF-M315E
Close-up of RLE Chemical 
Sensing Cable Drip Test (18 
MΩ Water). 
Colorimetric: Reagents Evaluated
Indicator Properties
Acros Universal pH Indicator 
Solution
Initial color is green. Color changes: pH 4.0 (red), pH 4.5 
(orange-red), pH 5.0 (orange), pH 5.5 (orange-yellow), pH 
6.0 (yellow), pH 6.5 (yellow-green), pH 7.0 (green), pH 7.5 
(green, slightly blue), pH 8.0 (green-blue), pH 8.5 (blue-
green), pH 9.0 (blue)
Bromocresol Green (Basic) Color change: pH 4.5 – 5.5 
Bromocresol Purple (Basic) Color change: pH 5.4 – 6.8
Bromothymol Blue (Basic) Color change: pH 6.0 – 7.6
Methyl Red (Basic) Color change: pH 4.8 – 6.0
Vanillin Changes color when reacted with various reagents
VWR Universal Indicator Initial color is green.  Color changes: pH 4.0 (red), pH 5.0 
(orange), pH 5.5 (orange-yellow), pH 6.0 (yellow-orange), pH 
6.5 (yellow), pH 7.0 (green), pH 7.5 (green-blue), pH 8.5 
(blue), pH 9.0 (blue-indigo), pH 9.5 (indigo), pH 10.0-11.0 
(violet)
Yamada Universal Indicator 
(Acidic)
Initial color is red.  Color changes: pH 4 (red), pH 5 (orange), 
pH 6 (yellow), pH 7 (green), pH 8 (blue), pH 9 (indigo), pH 10 
violet 
Yamada Universal Indicator 
(Neutral)
Initial color is green.  Color changes: pH 4 (red), pH 5 
(orange), pH 6 (yellow), pH 7 (green), pH 8 (blue), pH 9 
(indigo), pH 10 violet
Methyl Red – Solution/Wipe Tests
Methyl Red (Stock)
Methyl Red (Basic) – a) post-exposure, b) pre-
exposure, 
c) DI H2O
Methyl Red (Basic): 
Absorbent Materials
 Variety of materials tested
Fisher Filler Test – a) blank, b) pre-exposure, c) 
post-exposure (AF-M315E) and d) post-exposure 
(DI H2O)
Alumina Bead Test – a) blank, b) pre-exposure, c) 
post-exposure (AF-M315E)
and d) post-exposure (DI H2O)
Activated Alumina Test – a) blank, b) pre-exposure, 
c) post-exposure (AF-M315E)
and d) post-exposure (DI H2O)
3M Filler Test – a) blank, b) pre-exposure, c) 
post-exposure (AF-M315E)
and d) post-exposure (DI H2O)
Methyl Red (Basic): Absorbent 
Socks
• The final phase of testing for the 
development of a detection system 
for HAN/AF-M315E was performed 
by preparing different test samples 
using the most promising 
candidates from the absorbent 
materials testing and encasing 
them within a compatible material. 
– Activated alumina, pig powder, and 3M 
Filler material were selected for testing
• For the exposure test, 5 ml of AF-
M315E monopropellant was placed 
in a weigh boat and the “sock” to 
be tested was placed directly on 
the commodity. 
• After approximately one hour, the 
samples were removed from the 
weigh boats to determine if any 
monopropellant remained 
unabsorbed. 
Fisher Filler Test – a) blank, b) pre-exposure, c) post-exposure (AF-M315E)
Fisher Filler Test – a) pre-exposure, b) 40 mL AF-M315E, c) 40 mL DI H2O
Wipe Test – AF-M315E
• Using the Methyl Red (Basic) indicating wipes a test was conducted to 
determine the wipes effectiveness in detecting a small amount of residual 
propellant liquid from a surface
• The surface of several 3” x 2” stainless steel test panels were wetted 
using a swatch of the material saturated with AF-M315E or deionized 
water and then wiped using the indicating wipes
– As can be seen in the images, the wipes performed similarly to the drop test, showing a 
vivid color change upon direct exposure to the residual AF-M315E (Figure 39c). The 
deionized water control sample showed no change upon exposure, indicating that the 
indicating wipes are not susceptible to false positives from moisture. 
Methyl Red (Basic) Wipe Residue Test –
a) pre-exposure, 
b) AF-M315E Test Panel, 
c) post-exposure (AF-M315E), 
d) post-exposure (DI H2O). 
Ammonium Dinitramide – ADN
 Primary component of LMP-103S
 60%-65% is ADN
 “Green” Monopropellant LMP-103S
 Produced by Swedish Space Corporation (ECAPS)
 Successfully used in 2010 PRISMA mission
 Participant in F-16 Emergency Power Unit (EPU) test with Marshall Space Flight 
Center (MSFC)
ADN
COTS Sensors – Actively Pumped
 Multi-RAE Lite
 Active pumping
 Remote sensing
 3 sensors
 PID (VOC detection)
 Catalytic Bed (combustibles)
 Electrochemical (NH3)
 Wireless connectivity
 Data logging capabilities.
RAE Systems Multi-RAE Lite
 Dräger X-act 5000
 Active-pumping
 Reduces measurement time
 Variety of tubes for NH3  
detection 
 are available
 0.25 – 3 ppm, 0.05 – 10%, 
 2 – 30 ppm, 5 – 600 ppm,
 5 – 100 ppm
Dräger X-Act® 5000 
COTS Sensors – Diffusion-based
 GasAlert Extreme
 Diffusion-based
 0 – 100 ppm NH3 sensor
 -20 - 40°C, 15 – 90% humidity
 Water resistant
BW Technologies 
GasAlert Extreme Dräger Pac® 7000 
• Dräger Pac® 7000 
• Diffusion-based
• 0 – 300 ppm NH3 sensor
• -40 - 40°C, 700 – 1300 mbar
• Water resistant
Test Results – Actively Pumped
Setup for 
Evaluation of 
Active Sensors
Results from 0 – 10% Dräger-Tube® Evaluation
 RAE Systems MultiRAE Lite
 All three sensors (catalytic bed, ammonia, and PID) of the MultiRAE unit 
showed extremely high and rapid response when exposed to LMP-103S
 Three individual tests were run (although the last was shortened due to sensor 
saturation and the suspected possibility of damaging the electrochemical ammonia 
sensor) 
 Dräger X-act® 5000 (with Dräger-Tube®)
 A positive response was observed when exposed to LMP-103S
 The Dräger-Tubes® that were evaluated were the 5 – 600 ppm Ammonia Tube and the 
0.05 – 10% Ammonia Tube
 The 0.05 – 10% was the primary Dräger-Tube® that was evaluated due to the 
volatile nature of the propellant and the very high readings of ammonia 
previously observed using the MultiRAE Lite multigas sensor evaluation
Tests Results – Diffusion Based
Setup for 
Evaluation of 
Diffusion-based 
Sensors
 GasAlert Extreme 
 More consistent in the response upon exposure to the LMP-103S
 Response was very rapid in all three exposure tests (less than 15 seconds)
 Time for the system to return to baseline was quite long, taking over three hours 
 In addition to the results described above, the masses of each sample tested were monitored 
pre- and post-exposure in an attempt to determine the mass loss of propellant during each 
sample run. 
 Dräger X-act® 7000 (with Dräger-Tube®)
 A positive response was observed when exposed to LMP-103S
 This testing was done in concert with the testing of the GasAlert Extreme.
 As compared to the other passive gas sensor (GasAlert Extreme) the reproducibility of the 
Dräger Pac® 7000 seemed less consistent as that the time for the system to alarm varied 
considerably
 The Dräger Pac® 7000 still responded very quickly (all tests within 1 minute). The time for the 
system to return to baseline was also quite long, taking over three hours
Safety Considerations
 Hydroxylammonium Nitrate (HAN) based 
Monopropellant AF-M315E
 Safety glasses with side shields covered by a face shield
 Nitrile rubber gloves
 Flame retardant lab coat or coveralls
 Ammonium Dinitradmide (ADN) based 
Monopropellant LMP-103S
 Safety glasses with side shields with half-face respirator equipped 
with an organic cartridge 
 Alternative – full-face respirator equipped with an organic 
cartridge
 Nitrile rubber gloves
Conclusions
 Hydroxylammonium Nitrate (HAN) based 
Monopropellant AF-M315E
 Traditional vapor sensors ineffective
 Colorimetric detection system developed
 Absorbent “socks” and wipes prepared 
 Vacuum-sealed to keep prevent CO2 absorption
 Ammonium Dinitradmide (ADN) based Monopropellant 
LMP-103S
 Vapor sensors effective (both active and diffusion-based)
 MultiRAE Lite and GasAlert Extreme best performing 
 Stainless steel sensor wand added to MultiRAE Lite for remote sensing
Conclusions
 Detection Kits developed for both “green” monopropellants
Exterior of ADN/LMP-103S Kit
Exterior of HAN/AF-M315E Kit Interior of ADN/LMP-103S Kit
And so…


Familiarization and Detection of Green Monopropellants

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