A Linear Multiplexed Electrospray Thin Film Deposition System

Liquid spray is essential to industries requiring processes such as spray coating, spray drying, spray pyrolysis, or spray cooling. This thesis reports the design, fabrication, and characterization of a thin film deposition system which utilizes a linear multiplexed electrospray (LINES) atomizer. First, a thorough review of the advantages and limitations of prior multiplexed electrospray systems leads to discussion of the design rationale for this work. Next, the line of charge model was extended to prescribe the operating conditions for the experiments and to estimate the spray profile. The spray profile was then simulated using a Lagrangian model and solved using a desktop supercomputer based on Graphics Processing Units (GPUs). The simulation was extended to estimate the droplet number density flux during deposition. Pure ethanol was electrosprayed in the cone-jet mode from a 51-nozzle aluminum LINES atomizer with less than 3% relative standard deviation in the D10 average droplet diameter as characterized using Phase Doppler Interferometry (PDI). Finally a 25-nozzle LINES was integrated into a thin film deposition system with a heated, motion controlled stage, to deposit TiO2 thin films onto silicon wafers from an ethanol based nanoparticle suspension. The resulting deposition pattern was analyzed using SEM, optical profilometry, and macro photography and compared with the numerical simulation results. The LINES tool developed here is a step forward to enabling the power of electrospray for industrial manufacturing applications in clean energy, health care, and electronic

Fabrication and characterization of porous metal emitters for electrospray applications

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Aeronautics and Astronautics, 2008.Includes bibliographical references (leaves 137-140).Electrospray thrusters provide small, precise thrust with high power efficiencies and variable specific impulses from less than 1000s to over 4000s. The miniaturization and clustering of many emitters together is essential to increase the thrust density of electrospray devices in order to increase their domain of applicability in space. Electrospray emitter arrays have many advantages over existing electric propulsion devices including much lower mass per unit thrust and much lower volume per unit thrust than conventional ion and hall devices. Additionally, with emitter clustering, the thrust density can meet and even exceed that of hall or ion thrusters. A method of micro-fabricating electrospray emitter arrays using modified conventional microfabrication technology is presented. The method is adaptable to different emitter materials and can be used to create ultra dense emitter arrays with microfabrication precision down to the micron level. One-dimensional linear emitter arrays with emitter separation as low as 500 [mu]m have been fabricated out of porous tungsten and preliminary tests show that dense two-dimensional emitter arrays can be fabricated with emitter separations down to 300[mu]m. Experimental research that was conducted to characterize emitter array performance is also presented. Time of flight mass spectrometry was used to identify the emitted ion species from the device, which showed that the device operates in the ion emission regime. Current was collected as a function of applied voltage to show that the devices were able to operate with emitted current levels of 0.5 - 1.5 [mu]A per emitter, even for dense arrays. Direct thrust measurements were performed to show that the amount of thrust attainable is on the order of 0.1 [mu]N per [mu]A of emitted current for extraction voltages of around 1900 V.(cont.) A normalization scheme was implemented to compare performance of emitter arrays of different density and initial results from a numerical model has shown that the emitters might be limited by fluid transport.by Robert S. Legge Jr.S.M

Integrated out-of-plane nanoelectrospray thruster arrays for spacecraft propulsion

Nanoelectrosprays, well known for their use in sample injection for the mass spectrometry of large biomolecules, can also be used in other applications such as spacecraft propulsion. The thrust generated by a single electrospray emitter is well below 1 μN, which is several orders of magnitude below the required thrust for planned formation flying missions. This paper presents the process flow and the microfabrication of large 2D arrays of out-of-plane nanoelectrospray capillary emitters with integrated extractor electrodes as well as electrospray results. The capillaries, 70 μm high and with 24 μm inner diameter, are etched from one silicon-on-insulator wafer. The extractor electrodes are from another silicon-on-insulator wafer. Both parts are passively aligned to within 2 μm, centering each capillary under one extractor electrode, thus ensuring highly uniform emitter characteristics over large arrays. Low hydraulic impedance has been a major problem in out-of-plane electrospray designs in the past, which is solved here by adding a post-processing step in which the capillaries are filled with 5 μm silica microspheres fixed in place by silanization. Finally, this paper reports on successful spray tests carried out under vacuum conditions with single and arrays of capillaries spraying the ionic liquid EMI-Tf2 N demonstrating the operation of our nanoelectrospray thrusters in an ionic mode

Micromachined electrospray thrusters for spacecraft propulsion

Micromachining has enabled the downscaling of large, massive and power hungry systems into small batch-produced integrated devices. Recent progress in electrospray thruster technology, in particular the discovery of an ionic emission mode using the ionic liquid EMI-BF4 as fuel has sparked interest in miniaturizing this thruster technology, initially developed in the 1950's and lying dormant for several decades. Electrospray thrusters operate by applying a potential difference between a conductive liquid, usually on the tip of a needle or capillary, and an extractor electrode. Once a threshold voltage is reached the electric stress at the apex of the liquid surface overcomes surface tension and a spray of particles is ejected toward a counter electrode. The purely electrostatic nature of this type of thruster makes it an ideal candidate for miniaturization and the use of ionic liquids, also known as molten salts, as fuel allows operating the thruster in bipolar mode eliminating the need for an additional neutralizer. This thesis describes a process flow to fabricate planar arrays of silicon capillaries with integrated individual extractor electrodes. The developed process flow offers the possibility to manufacture arrays on the wafer scale allowing, in principle, to increase thrust from a fraction of micronewton for a single capillary to the millinewton level for large arrays. This process flow has been validated by microfabricating several thruster prototypes, which were packaged using Low Temperature Co-Fired Ceramic (LTCC) technology. In conjunction with this microfabrication process an onset voltage model was developed intended as design tool during thruster layout. This model allows to predict the voltage at which particle emissions initiate for complex geometries and to estimate the effect of dimensional variations on parameters such as crosstalk in large arrays. Tests carried out with thruster prototypes using single capillaries show a well defined energy distribution of the particles and the possibility to modulate spray current by changing the voltage. Controlled variations in the fluidic impedance of the emitters allow to spray in either ionic or droplet mode. Time-of-flight measurements with arrays show a beam composed of ions (monomers, dimers), thus yielding a high specific impulse. A first life test finally shows thruster operation for several hours with stable beam properties

Ionic liquid ion source emitter arrays fabricated on bulk porous substrates for spacecraft propulsion

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Aeronautics and Astronautics, 2011.Cataloged from PDF version of thesis.Includes bibliographical references (p. 305-321).Ionic Liquid Ion Sources (ILIS) are a subset of electrospray capable of producing bipolar beams of pure ions from ionic liquids. Ionic liquids are room temperature molten salts, characterized by negligible vapor pressures, relative high conductivities and surface tensions lower than water. Compared with the colloid form of electrospray, renowned for its applications to spectroscopy, ILIS yield highly monoenergetic beams composed entirely of ions. In this respect they are similar to Liquid Metal Ions Sources, but offer the ability to emit both positive and negative ions from a benign propellant that remains in the liquid state over a wide range of temperatures. When applied to spacecraft propulsion these sources are very power efficient and yield high specific impulses. Furthermore. the low flow rates and negligible vapor pressures of ionic liquids allow for passive feeding systems which can remain exposed to the vacuum of space. This configuration would remove the need for pressurized propellant tanks or valves, both of which are difficult to miniaturize for small satellites. However; the thrust produced from each emitter is very low, less than 0.1 [mu]N. As a result, compact arrays of active ILIS have been sought since their discovery. If arrays of modest packing density (~ 5 emitters/mm²) could be achieved, ILIS as thrusters would offer a scalable form of propulsion capable of providing useful thrust levels to small satellites with performance comparable to established, but difficult to miniaturize, plasma based ion engines. This research has sought a technique for creating arrays of ILIS from bulk porous substrates as part of an overall process for microfabricating complete thrusters. The thesis includes a survey of potential fabrication methods considering both suitability for forming arrays of ILIS and the ability to integrate each technique within a thruster packaging process. Electrochemical etching is highly selective and can proceed at rates which are limited by mass transport conditions. In this thesis we show how this etching regime can be exploited to smoothly remove material from the surface of a bulk porous metal substrate without damaging the internal pore structure. Dry film photoresists have been identified as a suitable alternative to spin on techniques for porous materials and have been applied within an electrochemical etching process. A two step process for forming arrays of ILIS has been motivated using numerical simulations of the etching process to predict emitter profiles and investigate the impacts of non-uniform etching conditions. These concepts have been applied experimentally using a custom built, automated, etching station capable of repeatedly producing arrays of 480 emitters spaced 500 pm apart on a 1 x 1 cm porous nickel substrate pre-mounted, and aligned, within a silicon thruster package. The emitters are typically 165 [mu]m tall with rounded tips suitable for operation as ILIS. Pulsed voltage conditions were found to significantly enhance wafer level uniformity enabling fabrication of functional emitters within a few hundred [mu]m of the substrate boundary. The structures have been smoothed and rounded, making them suitable for use as ILIS, during a secondary etch process using electrolytes doped with nickel chloride to suppress transient effects. These doped solutions enabled a few [mu]m of material to be removed selectively from the porous surface while maintaining smooth features. These arrays have been mounted and aligned with electrostatic grids to demonstrate their emission capabilities. Propellant has been fed to the emitters by capillarity within the porous bulk and then extracted at potentials as low as 850 V. Beam currents exceeding several 100 [mu]A at both positive and negative polarities have been measured using both EMIIm and EMI-BF₄ ionic liquid propellant. Two complete devices were tested yielding large beam currents and very high transmission fractions (- 88-100 %) from both attempts. We estimate that these devices can supply 10's of [mu]N of thrust at modest operating potentials, ~ 1.5 kV. with a specific impulse of roughly 2000-3000 s. When completely packaged, the thrusters measure 1.2 x 1.2 x 0.2 cm, weigh less than 1 g and require less than 0.65 W of operating power. These characteristics would be ideal for a small satellites where volume, mass and power are all at a premium, while the thrust levels would be sufficient to enable a variety of orbit variation and attitude control maneuvers. For example, applied to a CubeSat, this type of thruster system, including PPU, would occupy roughly 10 % of the spacecraft volume and mass while enabling de-orbiting from an 800 km altitude in roughly 100 days, compared with many years when left to decay naturally.by Daniel George Courtney.Ph.D

Design and fabrication of an integrated MEMS-based colloid micropropulsion system

The design, microfabrication and initial performance results of a prototype electrospray thruster with integrated individual extractor electrodes are reported in this paper. The aim was to demonstrate increased thrust with an array of emitters spraying simultaneously. Micromachining technologies were employed to achieve large emitter density per surface area, simple integration and good structural repeatability. The novelty of this work lies in the combination of high aspect ratio capillary emitters (height of 70 microns, inner diameter of 20 microns) with individual extractor electrodes having diameters from 80 microns upwards and a spacing as low as 25 microns from the capillary tips. The individual integrated electrodes, as opposed to the standard approach of one common electrode, allow for greater uniformity in critical voltages between capillaries and more finely modulated thrust control. Tests with the newly developed thrusters using the ionic liquid EMI-BF4 show that starting voltages below 700V and currents around 300nA per emitter can be achieved

Characterization of ionic liquid monopropellants for a multi-mode propulsion system

Multi-mode micropropulsion is a potential game-changing technology enabling rapidly composable small satellites with unprecedented mission flexibility. Maximum mission flexibility requires one shared propellant between the chemical and electric systems. A deep eutectic 1:2 molar ratio mixture of choline-nitrate and glycerol ([Cho][NO3] - glycerol) is investigated as a fuel component in a binary mixture propellant for such a multi-mode micropropulsion. Specifically, binary mixtures of the novel ionic liquid fuel with hydroxyl-ammonium nitrate (HAN) and ammonium nitrate (AN) are considered and compared against the previously investigated propellant [Emim][EtSO4]-HAN. Chemical rocket performance simulations predict this new propellant to have higher performance at lower combustion temperature, relaxing catalyst melting temperature requirements and making it a promising alternative. A qualitative investigation of synthesized propellants on a hot plate in atmosphere indicates the AN mixtures are significantly less reactive, and are therefore not investigated further. Quantitative reactivity studies using a microreactor indicate both 65:35% and 80:20% by mass [Cho][NO3] - glycerol to HAN propellants have a decomposition temperature 26-88% higher than [Emim][EtSO4]-HAN, depending on the catalyst material. The results indicate [Emim][EtSO4]-HAN with platinum catalyst is still most promising as a multi-mode micropropulsion propellant. Also, the linear burn rate of this monopropellant is determined to aid design of the microtube catalytic chemical thruster. With the design pressure of 1.5 MPa the linear burn rate of this propellant used for designing the multi-mode propulsion system is 26.4 mm/s. Based on this result, the minimum flow rate required is 0.31 mg/s for a 0.1 mm inner diameter feed tube and 3180 mg/s for a 10 mm inner diameter feed tube --Abstract, page iv

Comparing Direct and Indirect Thrust Measurements from Passively Fed and Highly Ionic Electrospray Thrusters

Highly ionic beams of several hundred microampere per squared centimeter have been measured from porous glass ionic liquid electrospray sources fabricated using a conventional mill. The thrust output from three prototype devices, two emitting the ionic liquid 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide and one emitting 1-ethyl-3-methylimidazolium-tetrafluoroborate, was measured directly using a precise balance. Thrusts up to 50μN were measured when emitting 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide in a bipolar, alternating potential configuration at less than 0.8 W input power and with propellant supplied from an internal reservoir. Measurements of mass spectra via time-of-flight spectrometry, angle resolved current distributions, ion fragmentation, and energy deficits have been applied to accurately calculate thrust and mass flow rates indirectly from the same devices. For two of the three cases, calculated and directly measured thrusts were in agreement to within a few micronewtons at input powers from 0.1 to 0.8 W. Emissions of 1-ethyl-3-methylimidazolium-tetrafluoroborate were shown to yield nearly purely ionic beams supporting high propulsive efficiencies and specific impulses of ∼65% and greater than 3200 s, respectively, at 0.5 W. Conversely, greater polydispersity was observed in 1-ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide emissions, contributing to reduced specific performance, ∼50% propulsive efficiency, and ∼1500s specific impulse at 0.5 W

DEVELOPMENT OF AN IONIC LIQUID FERROFLUID ELECTROSPRAY SOURCE AND MODE SHAPE STUDIES OF A FERROFLUID IN A NON-UNIFORM MAGNETIC FIELD

An electrospray source has been developed using a novel new fluid that is both magnetic and conductive. Unlike conventional electrospray sources that required microfabricated structures to support the fluid to be electrosprayed, this new electrospray fluid utilizes the Rosensweig instability to create the structures in the magnetic fluid when an external magnetic field was applied. Application of an external electric field caused these magnetic fluid structures to spray. These fluid based structures were found to spray at a lower onset voltage than was predicted for electrospray sources with solid structures of similar geometry. These fluid based structures were also found to be resilient to damage, unlike the solid structures found in traditional electrospray sources. Further, experimental studies of magnetic fluids in non-uniform magnetic fields were conducted. The modes of Rosensweig instabilities have been studied in-depth when created by uniform magnetic fields, but little to no studies have been performed on Rosensweig instabilities formed due to non-uniform magnetic fields. The measured spacing of the cone-like structures of ferrofluid, in a non-uniform magnetic field, were found to agree with a proposed theoretical model