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REPORT DOCUMENTATION PAGE Form Approved OMB No. 07040188 Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense, Washington Headquarters Services, Directorate for Information Operations and Reports (07040188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 222024302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DDMMYYYY) 3. DATES COVERED (From To) 2. REPORT TYPE Viewgraph January 2012 4. TITLE AND SUBTITLE EMllM Wetting Properties & Their Effect on Electrospray Thruster Design January 2012 March 2012 5a. CONTRACT NUMBER InHouse 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Garrett D. Reed 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 33SP0706 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NO. Air Force Research Laboratory (AFMC) AFRL/RQRS 1 Ara Drive. Edwards AFB CA 935247013 9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR S ACRONYM(S) Air Force Research Laboratory (AFMC) AFRL/RQR 5 Pollux Drive 11. SPONSOR/MONITOR S REPORT Edwards AFB CA 935247048 NUMBER(S) AFRLRZEDVG2012108 12. DISTRIBUTION / AVAILABILITY STATEMENT Distribution A: Approved for Public Release; Distribution Unlimited. PA#12264 13. SUPPLEMENTARY NOTES Conference paper for California State University Northridge, Northridge, California in 28 March 2012. 14. ABSTRACT Recent advances in the development of highly conductive ionic liquids have made them of interest for use as propellant in spacecraft propulsion systems. Electrospray thrusters apply strong electrostatic fields to an ionic liquid in order to extract and accelerate charged particles/droplets, producing thrust. The behavior of these ionic liquids as they pass through the components of an electrospray system can have a significant effect on thruster operation. The wetting and adhesion behavior between the ionic liquid propellant and solid materials can be characterized using the surface tension and contact or 'wetting' angle formed when a liquid droplet comes in contact with a solid surface. Ideally this angle is a function of the interactions between the solids surface energy, the surface tension of the liquid and the interactions of both with the surrounding medium. Deviation from ideal contact angle behavior can indicate surface inconsistencies, environmental effects or contamination of the solid and liquid. Contact angle and surface tension measurements are presented for the ionic liquid propellant 1Ethyl3 methylimidazolium bis(triuoromethylsulfonyl)imide, called EMIIm or EtMeImTf2N, with respect to various substrate materials and environmental conditions. Analysis of these measurements determines optimum materials and operating conditions for current and future electrospray thruster designs. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT a. REPORT Unclassified b. ABSTRACT Unclassified c. THIS PAGE Unclassified SAR 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON William Hargus 19 19b. TELEPHONE NO (include area code) 6612756799 Standard Form 298 (Rev. 898) Prescribed by ANSI Std. 239.18

EMIIM WETTING PROPERTIES & THEIR EFFECT ON ELECTROSPRAY THRUSTER DESIGN March 2012 Garrett D. Reed Professor Timothy Fox Professor Sydney Schwartz Dr. Michael Holmes California State University Northridge: Mechanical Engineering Department Air Force Research Laboratory: AFRL/RZSS DISTRIBUTION A: Approved for public release; distribution is unlimited.

Introduction Motivation & Objective Electrospray thruster for LISA Pathfinder DRS Payload Thruster failure mechanisms identified as dependant on wetting characteristics of propellant & component materials Wetting data needed to model these mechanisms & possible mitigation techniques Process for measuring amount of wetting Develop ideal method for measurement Determine uncertainties in measurement Test other ionic liquid (IL) propellants (BMIBG4, Air Force formulations ) Determine amount of wetting between thruster / propellant & relationship with failure mechanisms Photos Courtesy of Busek Co. Inc. DISTRIBUTION A: Approved for public release; distribution is unlimited 2

Electrosprays Emitter Internally / externally wetted, porous Allow propellant transport to tip Single Aperture 70x70 Array Extraction Grid Apply Lorentz force to propellant Extract ions / droplets depending on polarity Acceleration Grid Increase velocity of particles DISTRIBUTION A: Approved for public release; distribution is unlimited 3

Failure Mechanisms Bubble Formation Emitter Meniscus Pressure Grid Obstruction Grid Wetting Angle Arcing Between Grid & Emitter Emitter Tip Wetting Failure Mechanism Possible Wetting Solution DISTRIBUTION A: Approved for public release; distribution is unlimited 4

EMIIm Electrospray Propellant High conductivity / charge to mass ratio Neglible vapor pressure Low Viscosity Property Value Units Density (~20 C) 1523.6 kg m ³ Surface Tension 38.1 J m ² Expansion Coefficient (p) K ¹ Critical Temperature 1127 K Vapor Pressure Negligible Test Fluid Supplied by Strem Chemicals Inc. (CAS# 174899822) Factory sealed with dry nitrogen Water content (KarlFischer Titration) Factory Sealed Container: 2411±41 ppm Waste EMIIm exposed to ambient conditions for ~8 months: 2825 ±16 ppm Hygroscopic & Hydrophobic 1Ethyl3methylimidazolium bis(trifluoromethylsulfonyl)imide DISTRIBUTION A: Approved for public release; distribution is unlimited 5

Wetting Theory Idealized System: Smooth (Ra = 0) Cos ' rscos No chemical Reaction, inert components n No impurities present ' kt Chemically homogeneous components Constant temperature/pressure Eotvos No gravitational effects 2 3 V K Spherical droplet profile l T C T Young s Equation s sl sl Cos l l DISTRIBUTION A: Approved for public release; distribution is unlimited 6

Apparatus Chamber 8, AFRL Edwards AFB Two stage pump train (10 Torr) First Ten Angstroms (FTA125) Real time Sessile/pendant drop recording FTA32 analysis software, time resolved measurements: (t) & (t) DISTRIBUTION A: Approved for public release; distribution is unlimited 7

Methodology Simulate OnOrbit Electrospray Environment Determine Optimal Materials & Conditions Surface Tension Verify System Surface Tension Temperature Surface Tension Pressure Contact Angle Equilibrium Contact Angle Temperature Methodology Contact Angle (Sessile Drop Technique) Surface Tension (Pendant Drop Technique) Contact Angle Pressure Contact Angle Advancing/Receding DISTRIBUTION A: Approved for public release; distribution is unlimited 8

Substrates 0.634 1.20 2.52 Material Thickness (mm) Ra (μm) SS316 4.7 0.634/1.20/2.52 Fused Silica 0.5 < 0.144 Glass 1 < 0.144 Kapton 0.05 0.144 PTFE Teflon Ra Measured with an optical laser profilometer Limited resolution for smooth finishes PTFE Teflon 1.38 1.47 Pyrex 13 < 0.144 Tungsten 1 0.351 Silicon 0.5 < 0.144 Titanium 13 0.600 Titanium DISTRIBUTION A: Approved for public release; distribution is unlimited 9

Surface Tension I l = 38.1±1.09 (~25 C, 1 ATM) l V 2 3 Eotvos K T C T Surface Tension (l) Results 20 measurements taken at each temperature (T) Reasonable agreement with contemporary research / Model Decreasing l as T increases» should decrease as well DISTRIBUTION A: Approved for public release; distribution is unlimited 10

Surface Tension II Surface Tension (l) Results 8 measurements taken at each temperature (T) / Pressure (P) No meaningful trend measured Likely that properties change: Very small change with (P) Near transition state (hight / lowp) Change not measurable with this apparatus Two pressures tested: Ambient 760 Torr Vaccum 40 mtorr DISTRIBUTION A: Approved for public release; distribution is unlimited 11

Equilibrium Contact Angles I Dynamic Angle Behavior over Time Indicative of chemical reaction between componentcontaminants (Marmur et. al. / Kwok) Unstable angle follows power law over time ' kt Coefficients recorded for each substrate, varying T & P No measurable change in k(t, P) or n(t, P) n DISTRIBUTION A: Approved for public release; distribution is unlimited 12

Equilibrium Contact Angles II Material k n SS316 57.2 / 60.9 / 55.1 0.0055/0.0104/0.0285 Fused Silica 57.9 0.0281 Glass 45.6 0.0014 Kapton 59.3 0.0079 Pyrex 45.8 0.0336 Tungsten 39.1 0.0015 Silicon 56.4 0.0106 Titanium 63.2 0.0547 Material m b PTFE Teflon 75.9 Equilibrium Contact Angle Results Reaction affected each substrate except PTFE k appears to indicate initial contact angle n indicates rate of spreading Uncertainty between data sets: ± 4 Surface roughness appears to increase wetting DISTRIBUTION A: Approved for public release; distribution is unlimited 13

Advancing / Receding Angles I Approaches 0 Material Advancing Receding SS316 52.1 / 58.2 / 55.9 0 Fused Silica 51.6 0 Glass 55.2 0 Kapton 52.3 0 Pyrex 49.6 0 Tungsten 43.8 0 Silicon 48.0 0 Titanium 52.3 0 PTFE 68.3 56.6 DISTRIBUTION A: Approved for public release; distribution is unlimited 14

Temperature Effect l» sl Cos s sl l sl l l V 2 3 K T C T Equilibrium Temperature Effect Noticed over long equilibrium tests; drift in (T) Substrate temperature ramp, static equilibrium droplet Variation in (T), counterintuitive Temperature rises / Surface tension drops / Contact angle increases, greater change in adhesion tension DISTRIBUTION A: Approved for public release; distribution is unlimited 15

Conclusions and Future Work Conclusion Wetting properties measured on multiple EMIIm / solid material combinations PTFE alone exhibits high resistance to wetting / adhesion / chemical reaction Pyrex / Tungsten easily wetted by EMIIm Increase in surface roughness appears to increase rate of wetting Temperature decreases surface tension, ambiguous effect on wetting due to adhesion tension of the solid Future Work Repeat with other IL electrospray propellants Test more substrates, find a conductive solid with wetting properties similar to PTFE Include acid wash to clean substrate surface Reduce water content of EMIIm via titration process, increase accuracy Test EMIIm in electrospray at AFRL Acknowledgements Professor Timothy Fox, California State University Northridge Dr. William Hargus, AFRL / RZSS Edwards AFB CA DISTRIBUTION A: Approved for public release; distribution is unlimited 16

California State University Northridge Backup Slides: Surface Roughness 0 2 3 4mm mm 0 2 3 4 mm mm 0 2 3 4mm mm 0 0 0.45 0 0.5 0.5 0.06 0.5 0.4 0.5 0.35 0.4 0.05 1.5 1.5 0.3 1.5 0.35 2 0.04 2 0.25 2 0.3 0.25 2.5 0.03 0.2 2.5 2.5 0.2 0.15 3 0.02 3 3 0.15 0.1 3.5 3.5 3.5 0.1 0.01 0.05 0.05 4 4 4 0 0 0 mm mm mm 0.45 0 2 3 4mm IJm 0 2 3 4mm IJm 0 2 3 4 mm IJm 0 0 0 90 80 160 0.5 0.5 80 0.5 70 140 70 60 120 1.5 1.5 60 1.5 50 100 2 2 50 2 40 40 80 2.5 2.5 2.5 30 30 60 3 3 3 20 20 40 3.5 3.5 3.5 10 10 20 4 4 4 0 0 0 mm mm mm DISTRIBUTION A: Approved for public release; distribution is unlimited 17

California State University N orthridge Backup Slides: 8 Hour Test Contact Angle (EMIImSilicon)[Ambient Pressure/Temperature] 51 ' ': i...:... :~:... + : l : A i : ;.<.! i T. ' f. ttl! ~i 1't T 1 ~~~~ +... ~.L._. :,. I 50 ' ' '; i,, : '' ; '';,, + ' ~ ''.J..J).. i. 49 en Q)! 48, en Q) Q) 47 en c cc u 46 ~.. c 0 CJ 45 44.......,....,.....,. : I i _ ~.. : ~+ j i! + DISTRIBUTION A: Approved for public release; distribution is unlimited 1. i i t"t""""""""' +f..."'"+'"'"f""'f"'t"t"!"t"f"'"""""'"'f"""""f"""'!""'!"''f"'f"t t l + : i ; : :!!._,.. 8'= 53 2t(0.0198) ; +.. + ++++ t...,...,... + + ++ ++1 'T ;..;. :., :.., _,.. ' : ' : : ~~~~++~~~.:. :j_ ; ~ R = 2 0.992 H.; +.!. t' 1 ~ '..!. ' ' ' I +.;....;. ~ ~.., '~ _, t.., 1 i +.; ~ ' ~+~. ~ + 1 1 + '. 1 : ' : I. I :'.,. +... f ++i.. i.. t... +... +.. +.. +++ H1 " ' I' I : : I : ; +...... :.I :T ; ' T;!! I... +.. j.. +... c+i.. "'"f""'f"'t"t"h +... t... t... t'... t... t.. t.. t.. t l = 4... ' Ht! :;. = r...j.: r j + :lf : L : i i ':+...,...;... ++.. ++i.. cc+...;'...;... +.. i'.. +! +~ + :+...;... +!..+... f +++++...;... cc.;.... +.. + ++ H I!! '! ; :!!! i i i i :! f! r i! i :! i...;... + +++++...;...;... + + +H+I : i I I i,.. _, : f j..;.! ;! _,... L, 1 1 10 100 1000 10000 100000 Time (seconds) 18