Purdue University
On the Use of Fluorine‐Containing Nano‐Aluminum Composite Particles to Tailor Composite Solid Rocket Propellants
May 2022
Kyle Uhlenhake, Omar R. Yehia, Andrew Noel, Brandon C. Terry
Abstract
The burning rate of solid propellants is an important factor for optimizing rocket motors and improving performance. The enhanced burning rate can increase thrust and reduce a propulsion system‘s overall size and weight. In this study, a novel nano‐aluminum/THV composite additive was prepared and introduced into a solid ammonium perchlorate/polybutadiene composite solid rocket propellant to enhance its burning rate. The morphology of the composite particle additive and its effects on combustion were characterized. The use of small quantities (<15 wt.%) of the additive resulted in a burning rate enhancement of up to 2.1 times that of the conventional coarse aluminized propellant with a specific impulse loss of only 3 seconds, and as much as 4.7 times enhancement with a predicted loss of 22 seconds in theoretical specific impulse. Some of this loss may be recovered by the improved combustion efficiency in smaller rocket motors because the additive was shown to significantly reduce the aluminum agglomeration at the propellant burning surface and reduce the size of reaction products which may reduce two‐phase flow losses. The additive also provides wide burning rate tailorability, favorable for motor, grain, and thrust curve design. The burning rate enhancement mechanism is thought to be a physical cratering mechanism governed by the burning rate disparity between the binder/oxidizer system and the nano‐aluminum/fluoropolymer additive and not a chemical catalytic effect.
Modifying burning rate and agglomeration size in aluminized composite solid propellants using mechanically activated metals
December 2016
DOI: https://docs.lib.purdue.edu/open_access_dissertations/975/
Hatem Mohamed Belal
Abstract
Agglomeration reduction techniques are important field in solid propellant industry, Large agglomeration results in excessive two phase losses. Tailored composite particles has been applied to tailor aluminum particle ignition and combustion. In this research, mechanical activated aluminum magnesium powders are synthesized, tested in both laser ignition using CO2 and propellant. Prepared powders categorized into particle size that suitable for propellant application. Laser ignition tests showed that the prepared powder are more reactive than magnalium which has the same Al:Mg weight ratio. Agglomeration capturing showed that the prepared powder produce much less than neat aluminum or even similar physical mixture of aluminum and magnesium. The burning rate of propellant using the prepared powder is increased.
MA Al/Mg powders as long as with comparable physical mixture are applied in propellant formulation with AP/HTPB. In order to quantify the effect of changing Mg percent. Burning rate is measured from videos captured for strand burning in windowed pressure vessel, also the agglomeration was capturing using special setup. The results showed that MA powder increase burning rate and this increase reach maximum at 50% Mg, while propellant using physical mixture of Al/Mg show constant or little decrease in burning rate. In addition, the MA powder show lower agglomeration size in comparison to neat aluminum propellant or physical mixture with the same Mg percent. The lowest agglomeration sizes were for MA50. However, equilibrium calculation showed 4 sec losses in specific impulse, so MA 70 was chosen as a compromise between low agglomeration size at the minimum loss in specific impulse.
Magnalium is an alloy of aluminum and magnesium and it is known for its ease of ignition and high oxidation energy content. It has been used as a metal fuel to increase burning rates of composite modified double base (CMDB) and ammonium perchlorate (AP) composite propellants. However, the ignition temperature is larger than the comparable mechanically activated (MA) Al-Mg powder.
Mechanical milling was performed on magnalium powders and modifications of structure and morphology of the alloy during milling were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The prepared magnalium powder was used in a solid propellant, which showed higher burning rates than those containing as-received magnalium. Furthermore, milled magnalium showed higher agglomeration reduction than both as received magnalium as well as MA Al-Mg powders.
Extend the application of mechanical alloying of aluminum to other metals with extreme difference in melting/ boiling temperature, the first is Zirconium which is a long time candidate in solid propellant community. The ease of zirconium ignition and the micro-explosive behavior shown by neat zirconium particles promote its usage in agglomeration reduction effort. the other metal is Indium, which has very low melting point compared to other metal, this may open the possibility of earlier reaction of aluminum particles at or near propellant surface resulting in less pre ignition time which reduce agglomeration tendency.
MA of 90% Aluminum and 10% of Zirconium or 10% Indium using High energy ball milling, particle characterization using SEM/FIB, XRD and DSC/TGA are performed, burning rate and agglomeration size analyses of solid propellant using sieved MA-powder are done. The results showed that the both MA Al-ZR and MA Al-In ignite in laser beam which verify change in reactivity from neat aluminum with its protective alumina coating. However, burning rate results show no change in burning rate from neat aluminum, also the prepared material shows no reduction in agglomeration sizes.
Additively Manufactured Micro- and Nano- Al/PVDF Ignition Sensitivity and Burning Characterization
DOI: doi.org/10.1002/prep.202200204
Kyle E. Uhlenhake, Diane N. Collard, Alexander C. Hoganson, Alex D. Brown, Sara Fox, Metin Örnek, Jeffrey F. Rhoads and Steven F. Son
Abstract
Aluminum (Al) and polyvinylidene fluoride (PVDF) composites can be used in many unique applications in the field of energetic materials. Due to their low melting point, many PVDF composites can be additively manufactured. However, more research is needed to better understand the ignition and combustion of these materials. Manipulating the size of aluminum (Al) particles in Al/PVDF composites can drastically alter the burning rate, ignition characteristics, and possibly flame temperatures. This study characterizes the ignition of additively manufactured microand nano- Al/PVDF composites through hotwire ignition tests. Both nAl and μAl particles were mixed in PVDF at 20 wt.% and additively manufactured into disks via fused filament fabrication. The nAl/PVDF printed disks ignited at a minimum ignition power (MIP) of 4.1 W compared to the 9.5 W required for ignition of μAl/PVDF disks. At identical powers, ignition delays were significantly shorter for nAl/PVDF disks. Additionally, while the nAl/PVDF disks reacted instantaneously at any power above their MIP, the μAl/PVDF disks exhibited smaller, localized flames before complete combustion, if the power was below 17.5 W. Flame temperatures were estimated through three-color pyrometry and compared to thermochemical equilibrium calculations. While theoretical flame temperatures for nAl/PVDF and μAl/PVDF are 2023 K and 2314 K respectively, both samples burned near 2000 K when measured using pyrometry.
Photoflash and laser ignition of Al/PVDF films and additively manufactured igniters for solid propellant
October 2022
DOI: https://www.sciencedirect.com/science/article/abs/pii/S001021802200267X?via%3Dihub
Diane N. Collard, Kyle E. Uhlenhake, Metin Örnek, Jeffrey F. Rhoads and Steven F. Son
Abstract
Solid propellants are employed in a range of applications from the inflation of airbags to propulsion systems for rockets. The ignition of solid propellants must be carefully controlled and modified on a per-use basis due the specific ignition requirements of each application. Using tailored photoreactive materials as a source of ignition for solid propellants, or other energetic materials, could reduce the added weight and risk of traditional initiators and result in safer, more effective solid rocket motor ignition systems. This study demonstrates the tunability of the ignition delay and propagation properties of optically-sensitive, nearly full density reactive aluminum/polyvinylidene fluoride (Al/PVDF) films and additively manufactured igniters. A single printed layer of pure nano-aluminum (nAl) at ideal stoichiometry in PVDF was found to flash ignite, but frequently yielded delayed transitions in steady propagation from the igniter to the propellant. To improve the continuity and steadiness of the transition, fuel particle size, igniter thickness, and a combination of layers of nAl and micron-sized aluminum (μAl) were investigated. In printed igniters with layers of μAl, only a single layer of nAl was needed to flash ignite the material and propagate to the layers of μAl without delay. For igniters cast onto strands of ammonium perchlorate composite propellant, continuous ignition was achieved with a single layer of nAl printed atop a triple layer of μAl for the flash-activated igniters and a single layer of nAl printed atop a single and triple layer of μAl for laser-driven igniters. The nAl/PVDF layer enabled good flash or laser ignition sensitivity, while the μAl/PVDF produced more sustained heat transfer to produce a reliable ignition process.
Characterization of an Aluminum–Lithium-Alloy-Based Composite Propellant at Elevated Pressures
October 2020
DOI: https://arc.aiaa.org/doi/10.2514/1.B37848
Gabriel A. Diez, Timothy D. Manship, Brandon C. Terry, Ibrahim E. Gunduz and Steven F. Son
Abstract
Aluminum (Al)/lithium (Li)-alloy-based fuels can potentially improve composite propellant performance and reduce hydrochloric acid formation. Shattering microexplosions have been observed in Al–Li-based composite propellants at 0.1 MPa; however, combustion characterization of Al–Li-based propellant as a function of pressure has not been performed previously. Measurement of the burning rate of an Al–Li composite propellant and quantification of agglomerate production near the propellant surface at various pressures are presented in this work. Al–Li particle agglomeration, determined to be unconsumed Al–Li, increased with increasing pressure, suggesting that microexplosions were inhibited at higher pressures. Burning rate experiments demonstrated a plateau burning rate effect that occurred in propellant with fine grade (mean diameter: 17 μm) Al–Li particles, whereas the as-received Al–Li-containing (mean diameter: 53 μm) propellant maintained a constant pressure exponent of about 0.39 over all pressures tested. The finer Al–Li propellant had a pressure exponent of 0.59 at pressures below about 4 MPa and a pressure exponent of 0.11 above 4 MPa. Surface imaging of the Al–Li propellant showed a distinctive condensed phase reaction on the surface, which became more prominent with the finer Al–Li particles and at higher pressures: a potential source of the plateau burning rate effect.
Characterization of the influence of aluminum particle size on the temperature of composite-propellant flames using CO absorption and AlO emission spectroscopy
2021
DOI: https://www.sciencedirect.com/science/article/abs/pii/S1540748920302492?via%3Dihub
Morgan D. Ruesch, Austin J. McDonald, Garrett C. Mathews, Steven F. Son, Christopher S. Goldenstein
Abstract
Understanding the temperature of aluminized, composite-propellant flames is critical to achieving robust rocket motor designs and developing accurate, predictive models for propellant combustion. This work presents measurements of (1) the temperature of CO (within the flame bath gas) and (2) the temperature of AlO (located primarily within regions surrounding the burning aluminum particles) within aluminized, composite-propellant flames as a function of height above the burning propellant surface. Three aluminized, ammonium-perchlorate (AP), hydroxyl-terminated polybutadiene (HTPB) composite propellants with varying aluminum particle size (nominally 31 �m, 4.5 �m, or 80 nm) and one non-aluminized AP-HTPB propellant were studied while burning in air at 1 atm. A wavelength-modulation-spectroscopy technique was utilized to measure CO temperature and mole fraction via mid-infrared wavelengths and a conventional AlO emission-spectroscopy technique was utilized to measure the temperature of AlO. The bath-gas temperature varied significantly between propellants, particularly within 2 cm of the burning surface. The propellant with the smallest particles (nano-scale aluminum) had the highest average temperatures and far less variation with measurement location. At all measurement locations, the average bath-gas temperature increased as the initial particle size of aluminum in the propellant decreased, likely due to increased aluminum combustion. The results support arguments that larger aluminum particles can act as a heat sink near the propellant surface and require more time and space to ignite and burn completely. On a time-averaged basis, the temperatures measured from AlO and CO agreed within uncertainty at near 2650 K in the nano-aluminum propellant flame, however, AlO temperatures often exceeded CO temperatures by ≈ 250 to 800 K in the micron-aluminum propellant flames. This result suggests that in the flames studied here, and on a time-averaged basis, the micron-aluminum particles burn in the diffusion-controlled combustion regime, whereas the nano-aluminum particles burn within or very close to the kinetically controlled combustion regime.
Agglomerate Sizing in Aluminized Propellants Using Digital Inline Holography and Traditional Diagnostics
April 2018
DOI: https://doi.org/10.2514/1.B36859
Michael S. Powell, Ibrahim W. Gunduz, Weixiao Shang, Jun Chen, Steven F. Son, Yi Chen and Daniel R. Guildenbecher
Abstract
Aluminized ammonium perchlorate composite propellants can form large molten agglomerated particles that may result in poor combustion performance, slag accumulation, and increased two-phase flow losses. Quantifying agglomerate size distributions are needed to gain an understanding of agglomeration dynamics and ultimately design new propellants for improved performance. Due to complexities of the reacting multiphase environment, agglomerate size diagnostics are difficult and measurement accuracies are poorly understood. To address this, the current work compares three agglomerate sizing techniques applied to two propellant formulations. Particle collection on a quench plate and backlit videography are two relatively common techniques, whereas digital inline holography is an emerging alternative for three-dimensional measurements. Atmospheric pressure combustion results show that all three techniques are able to capture the qualitative trends; however, significant differences exist in the quantitative size distributions and mean diameters. For digital inline holography, methods are proposed that combine temporally resolved high-speed recording with lower-speed but higher spatial resolution measurements to correct for size–velocity correlation biases while extending the measurable size dynamic range. The results from this work provide new guidance for improved agglomerate size measurements along with statistically resolved datasets for validation of agglomerate models.
Microexplosions and ignition dynamics in engineered aluminum/polymer fuel particles
February 2017
DOI: https://www.sciencedirect.com/science/article/abs/pii/S0010218016303078?via%3Dihub
Mario A. Rubio, I. Emre Gunduz, Lori J. Groven, Travis R. Sippel, Chang Wan Han, Raymond R. Unocic, Volkan Ortalan, Steven F. Son
Abstract
Aluminum particles are widely used as a metal fuel in solid propellants. However, poor combustion efficiencies and two-phase flow losses result due in part to particle agglomeration. Recently, engineered composite particles of aluminum (Al) with inclusions of polytetrafluoroethylene (PTFE) or low-density polyethylene (LDPE) have been shown to improve ignition and yield smaller agglomerates in solid propellants. Reductions in agglomeration were attributed to internal pressurization and fragmentation (microexplosions) of the composite particles at the propellant surface. Here, we explore the mechanisms responsible for microexplosions in order to better understand the combustion characteristics of composite fuel particles. Single composite particles of Al/PTFE and Al/LDPE with diameters between 100 and 1200 µm are ignited on a substrate to mimic a burning propellant surface in a controlled environment using a CO2 laser in the irradiance range of 78–7700 W/cm2. The effects of particle size, milling time, and inclusion content on the resulting ignition delay, product particle size distributions, and microexplosion tendencies are reported. For example particles with higher PTFE content (30 wt%) had laser flux ignition thresholds as low as 77 W/cm2, exhibiting more burning particle dispersion due to microexplosions compared to the other materials considered. Composite Al/LDPE particles exhibit relatively high ignition thresholds compared to Al/PTFE particles, and microexplosions were observed only with laser fluxes above 5500 W/cm2 due to low LDPE reactivity with Al resulting in negligible particle self-heating. However, results show that microexplosions can occur for Al containing both low and high reactivity inclusions (LDPE and PTFE, respectively) and that polymer inclusions can be used to tailor the ignition threshold. This class of modified metal particles shows significant promise for application in many different energetic materials that use metal fuels.
Combustion of Bimodal Aluminum Particles and Ice Mixtures
January 2012
Terrence L. Connell, Jr., Grant A. Risha, Richard A. Yetter, Vigor Yang, & Steven F. Son
Abstract
The combustion of aluminum with ice is studied using various mixtures of nano- and micrometersized aluminum particles as a means to generate high-temperature hydrogen at fast rates for propulsion and power applications. Bimodal distributions are of interest in order to vary mixture packing densities and nascent alumina concentrations in the initial reactant mixture. In addition, the burning rate can be tailored by introducing various particle sizes. The effects of the bimodal distributions and equivalence ratio on ignition, combustion rates, and combustion efficiency are investigated in strand experiments at constant pressure and in small lab-scale [1.91 cm (0.75 in.) diameter] static firedrocket-motor combustion chambers with center-perforated propellant grains. The aluminum particles consisted of nanometer-sized particles with a nominal diameter of 80 nm and micron-sized particles with nominal diameters of 2 and 5 μm. The micron particle addition ranged from 0% to 80% by active mass in the mixture. Burning rates from 1.1 (160 psia) to 14.2 MPa (2060 psia) were determined. From the small scale motor experiments, thrust, C*, Isp, and C* and Isp efficiencies are provided. From these results, mechanistic issues of the combustion process are discussed. In particular, overall lean equivalence ratios that produce flame temperatures near the melting point of alumina resulted in considerably lower experimental C* and Isp efficiencies than equivalence ratios closer to stoichiometric. The infstitution of micron aluminum for nanometer aluminum had little effect on the linear burning rates of Al/ice mixtures for low-mass infstitutions. However, as the mass addition of micron aluminum increased (e.g., beyond 40% 2-μm aluminum in place of 80-nm aluminum), the burning rates decreased. The effects of bimodal aluminum compositions on motor performance were minor, although the experimental results suggest longer combustion times are necessary for complete combustion.
CuO/Al Igniters For Solid Rocket Motor Ignition
September 2013
DOI: https://www.researchgate.net/publication/269567051_CuOAl_Thermites_for_Solid_Rocket_Motor_Ignition
David A. Reese; Darren M. Wright; Steven Son
Abstract
A safe, fast, repeatable means of ignition is required for lab-scale solid rocket motor test experiments. To prevent early burn data from being obscured, an energetic compound with a high reaction rate is needed. A thermite mixture based on micron copper (II) oxide and micron aluminum was chosen for this purpose. This work investigates the efficacy of CuO/Al thermites for lab-scale rocket motor ignition, including experiments on safety testing, packaging, initiation, igniter size determination, and hot fire testing. The end result is a safe, inexpensive, efficient, and readily available method of igniting lab-scale solid rocket combustors.
Further Development of an Aluminum and Water Solid Rocket Propellant
July 2011
David E. Kittell, Timothée L. Pourpoint, Lori J. Groven, and Steven F. Son
Abstract
Nanoscale aluminum and water has been used as a stepping stone towards in-situ rocket propellants and as a testbed for nanoenergetic composite propellants. A baseline formulation of nanoscale aluminum and water was developed and demonstrated with a sounding rocket flight in 2009. Performance of the propellant was not optimized, hence a reformulation was sought with an emphasis on improved safety and more efficient combustion. The chosen reformulation is a bimodal powder distribution of 70 wt.% Novacentrix 80 nm Al and 30 wt.% Valimet 2 μm Al at an equivalence ratio of 0.813 (optimized for sea level Isp). The mixture also includes 3 wt.% ammonium dihydrogen phosphate, to inhibit the slow reaction of nanoaluminum with water, and 1 wt.% polyacrylamide to improve material suspension. Ammonium dihydrogen phosphate can protect nanoaluminum in solution for several hours, but degradation can occur while mixing, and pH increases from slightly acidic to basic with increased mixing time and temperature. The stress of mixing might be removing the coating and exposing nanoaluminum to water. It is also shown that nanoaluminum reacts faster in basic aqueous solutions than in solutions with neutral pH. Static motor tests reveal that propellant formulations with neutral pH provide better performance. Implementations of shorter mixing times and reduced temperatures are used to control the pH of the propellant, resulting in increased Isp values of as much as 30%. © 2011 by the American Institute of Aeronautics and Astronautics, Inc.
Other Universities
Effect of Initial Reactant Temperature on Flame Speeds in Aluminum Dust Suspensions
October 2020
DOI: https://www.tandfonline.com/doi/abs/10.1080/00102202.2020.1820496?journalCode=gcst20
Frederic Blais, Philippe Julien, Jan Palecka, Samuel Goroshin, Jeffrey M. Bergthorson
Abstract
Measurements of how the flame speed in suspensions of metal fuels depends on the initial temperature of the unburned mixture are important for understanding the role of mixture preheat by radiation heat transfer. This preheat can be an important stabilization mechanism for metal dust flames in energetic devices. A newly constructed counter-flow flat-flame metal dust burner allows for the measurement of burning velocities in aluminum-air suspensions preheated to temperatures up to 524 K using Particle Image Velocimetry (PIV). The experimental method was verified by measuring and comparing burning velocities in preheated methane-air mixtures at different fuel-oxygen equivalence ratios with previous experimental data and theoretical predictions. Whereas the flame speed in methane-air mixtures increases by 2.75 times with an increase in temperature to about 524 K, the flame speed in aluminum-air mixtures increases by less than 2 times over the same temperature interval. The independence of the adiabatic flame temperature of aluminum-air flames on the initial temperature of the mixture suggests practically constant reaction rates either for kinetically- or diffusion-controlled aluminum combustion. Thus, the observed moderate dependence of the aluminum-air flame speed on mixture initial temperature can be explained by a cumulative effect of the increased heat diffusivity, decrease in the amount of heat required to reach the particle ignition temperature, and increased flame sensitivity to preheat due to discrete source effects discussed in recent flame models.
A correlation for burn time of aluminum particles in the transition regime
2009
DOI: https://doi.org/10.1016/j.proci.2008.06.205
Patrick Lynch, Herman Krier, Nick Glumac
Abstract
A study of the combustion times for aluminum particles in the size range of 3–11 lm with oxygen, car[1]bon dioxide, and water vapor oxidizers at high temperatures (>2400 K), high pressures (4–25 atm), and oxidizer composition (15–70% by volume in inert diluent) in a heterogeneous shock tube has generated a correlation valid in the transition regime. The deviation from diffusion limited behavior and burn times that could otherwise be accurately predicted by the widely accepted Beckstead correlation is seen, for example, in particles below 20 lm, and is evidenced by the lowering of the diameter dependence on the burn time, a dependence on pressure, and a reversal of the relative oxidizer strengths of carbon dioxide and water vapor. The strong dependence on temperature of burn time that is seen in nano-Al is not observed in these micron-sized particles. The burning rates of aluminum in these oxidizers can be added to predict an overall mixture burnout time adequately. This correlation should extend the ability of mod[1]elers to predict combustion rates of particles in solid rocket motor environments down to particle diameters of a few microns.
Emission and Laser Absorption Spectroscopy of Flat Flames in Aluminum Suspensions
June 2017
DOI: https://doi.org/10.1016/j.combustflame.2017.03.006
Michael Soo, Samuel Goroshin, Nick Glumac, Keishi Kumashiro, James Vickery, David L. Frost, Jeffrey M. Bergthorson
Abstract
Imaging emission spectroscopy, spatially resolved laser-absorption spectroscopy, and particle image velocimetry (PIV) are applied to a flat flame stabilized in a suspension of micron-sized aluminum. The results from the combination of diagnostics are used to infer the combustion regime of the particles and to estimate the characteristic combustion time of the suspension. It is observed that the reaction zone of the flame in stoichiometric aluminumair suspensions exhibits strong self-reversal of the atomic aluminum emission lines. These lines also exhibit high optical depths in both emission and absorption spectroscopy. The strong self-reversal and high optical depths indicate high concentrations of aluminum vapor within the reaction zone of the flame at multiple temperatures. These features provide evidence of the formation of vapor-phase micro-diffusion flames around the individual particles in the suspension. In aluminum-methane-air flames, the lack of self-reversal and lower optical depths of the aluminum atomic lines indicate the absence of vapor-phase micro-diffusion flames, and point to a more heterogeneous, and likely kinetically-controlled, particle combustion regime. The reaction zone thickness is estimated from the spatially resolved profiles of aluminum resonance lines in both absorption and emission through the flame. The emission measurements yield a reaction zone thickness on the order of 1.7±0.3 mm in aluminum-air flames, and the absorption measurements yield a thickness on the order of 2.3±0.5. It is demonstrated that the combination of the combustion zone thickness measurement, flame temperatures determined from molecular AlO emission spectra, and particle velocity measurements from the PIV diagnostic permits an estimation of the burning time in the suspension. The burning time in stoichiometric aluminum-air suspensions using the suite of diagnostics is estimated to be on the order of 0.7 milliseconds.
Aluminum-propane-air hybrid fames in a Hele-Shaw cell
2021
DOI: 10.1016/j.proci.2020.09.017
Jan Palečka, Judy Park, Samuel Goroshin, Jeffrey M Bergthorson
Abstract
This paper introduces a novel Hele-Shaw cell apparatus to be used for the study of propagation and stability phenomena in heterogeneous flames. In particular, the apparatus is used to experimentally examine the coupling/decoupling of dual-front flames propagating in suspensions of micron-size aluminum particles in propane-air gas mixtures at varying gas equivalence ratios and aluminum concentrations. The results show that the thermal coupling that exists between the primary propane-air flame front and the secondary aluminum flame front is a strong function of the rate of reaction, and of the temperature, of the secondary front and much less dependent on the reaction rate or temperature of the primary front. It is also shown that flame instabilities in hybrid aluminum-propane-air flames significantly increase the flame surface area, enhance the propagation rate, and can also exhibit complex interactions with front coupling.
Some fundamental aspects of laminar flames in nonvolatile solid fuel suspensions
2021
DOI: https://doi.org/10.1016/j.pecs.2022.100994
Samuel Goroshin, Jan Palečka, Jeffrey M. Bergthorson
Abstract
This paper critically reviews the theoretical and experimental literature regarding the fundamental aspects of flames in nonvolatile solid fuel suspensions. Unlike volatile fuels that form continuous premixed gaseous flame sheets, flame fronts in nonvolatile suspensions are driven by heterogeneous reactions localized on the surface, or near the surface, of individual particles. Practically all peculiarities of heterogeneous flames can be linked to this “flame-inside-the-flame” combustion front structure. These localized reactions enable particles to self-heat and transition from kinetically to diffusion-limited heterogeneous reaction during the process of particle ignition. After ignition, burning particles behave as individual diffusion micro-reactors that are insensitive to the bulk gas temperature and overall heat loss from the system. Relatively small quenching distances of the flame in suspensions, long plateaus in the dependence of burning velocity on fuel concentration stretching to very fuel-rich mixtures, and the discrete flame propagation regime, where burning velocity is insensitive to particle combustion time and the flame-front structure is rough and nonuniform, are all manifestations of particle ignition and combustion in the diffusion-limited regime. This review summarizes the key experimental evidence of laminar flame structure and flame speed from a variety of experimental apparatus both in the laboratory and under microgravity conditions, and interprets these results in terms of relatively simple theoretical models. Heterogeneous flames are observed to exhibit many of the thermodiffusive and hydrodynamic instabilities of homogeneous flames, as well as several new instabilities that arise from the multiphase nature of the fuel and particle ignition and extinction. Flames of binary mixtures of heterogeneous fuels, or gaseous and solid fuel mixtures, are also reviewed and it is shown that a simple model based on matching the flame speed between thermally interacting fronts can capture the key physics. Finally, the last chapter of the review discusses why the important or even crucial role of radiation heat transfer predicted by theoretical models for flames in suspensions is not supported by the available experimental evidence. It is argued that large spatial scales of radiation heat transfer do not permit separation of the radiation transfer problem from boundary conditions and flow configuration, making one-dimensional flame models that include radiation inadequate for the description of flames in the laboratory and even in relatively large unconfined dust clouds.
Detonation of mixtures of nanometric or flake aluminum with water
2021
Link: https://escholarship.mcgill.ca/concern/theses/9w032781h
Geoffrey Chase, David Frost
Abstract
The detonation of suspensions of nanometric and flake aluminum powders mixed with aqueous solutions of dilute hydrogen peroxide (H2O2) was experimentally investigated. The nano-Al powder was coated with 8–10 wt% Viton and had a nominal diameter of 91 ± 27 nm. The flake-Al powder was coated with 10 wt% trimethylolpropane trimethacrylate and had a surface area of 5.09 m2/g. Detonation velocity and cylinder wall expansion tests were conducted in aluminum- and PVC-encased charges measured with shock pins and photonic Doppler velocimetry. Mixtures containing aqueous solutions of 10–20 wt% H2O2 detonated at 2.9–3.5 km/s, with variations in the detonation velocity attributed to variations in time-dependent density. Mixtures containing 10 wt% H2O2 solutions did not consistently detonate, indicating that porosity from hydrogen peroxide decomposition has a sensitizing effect. Mixtures containing only distilled water, 5 or 7.5 wt% H2O2 solutions, dilute ammonium nitrate solutions, glass microballoons, or micron-scale spherical aluminum powder failed to sustain detonation, but could potentially sustain detonation with optimization of the shot processing.
Coaxial laser absorption and optical emission spectroscopy of high-pressure aluminum monoxide
April 2022
https://doi.org/10.1364/OL.456342
K. A. Daniel, C. M. Murzyn, D. J. Allen, K. P. Lynch, C. R. Downing, and J. L. Wagner
Abstract
This work advances laser absorption spectroscopy with measurements of aluminum monoxide (AlO) temperature and column density in extreme pressure (P > 60 bar) and temperature (T > 4000 K) environments. Measurements of the AlO A 2Πi–X 2Σ + transition are made using a micro[1]electromechanical system, tunable vertical cavity surface emitting laser (MEMS-VCSEL). Simultaneous emission measurements of the AlO B 2Σ +–X 2Σ + transition are made along a line of sight that is coaxial with the laser absorption. Absorption temperature fits agree with emission spectra for a T =3200 K, P=9 bar case. In cases with T > 4000 K, P > 60 bar, absorption fits match the ambient temperature while emission fits over-estimate it, owing to high optical depths. These data juxtapose passive and active spectro[1]scopic methods and demonstrate the versatility of AlO laser absorption in high-pressure and high-temperature environments where experimental data remain scarce, and engineering models will benefit from refined measurements.
Experimental investigation of aluminum-air burning velocity at elevated pressure
February 2023
DOI: https://doi.org/10.1016/j.combustflame.2022.112532
G. Foster, N.J. Kempema, J.E. Boyer, J.R. Harris, R.A. Yetter
Abstract
Aluminum is an energy-dense metal that reacts exothermically with a range of oxidizers, making it a potentially useful fuel for certain thermal energy and power applications (e.g., boilers, swirl-stabilized burners, rockets, etc.). In addition to its reactive properties, aluminum is naturally abundant and commercially available in fine powders that are relatively inexpensive and chemically stable. Fine aluminum dusts, with particle diameters on the order of micrometers, can be aerosolized and mixed with a gaseous oxidizer such as air to create stable dust flames and heat for a thermodynamic cycle. In order to realize the potential utility of aluminum-air dust flames, the fundamental combustion behavior, such as the burning velocity, must be understood. In this work, an experimental system was developed that allows metal dust flames to be observed within an optically-accessible pressurized chamber. Using a high-speed camera, fuel-rich premixed aluminum-air jet flames were imaged through narrowband interference filters, and the data were used to calculate burning velocity. A single polydisperse size distribution of particles was tested at pressures ranging from 1 to 7.2 bar. Burning velocity was found to decrease with increased pressure (P), with an approximate proportionality to P−0.6 over the range of pressures tested (∼P−0.3 for only the laminar flow conditions). This reduction in burning velocity with increased pressure is hypothesized to occur due to increased oxidizer density along with a decrease in interparticle spacing, which may result in asymmetric particle heating and increased competition for oxidizer.
The effect of surface modification of aluminum powder on its flowability, combustion and reactivity
December 2010
DOI: https://www.sciencedirect.com/science/article/abs/pii/S0032591010003645
Laila J. Jallo, Mirko Schoenitz, Edward L. Dreizin, Rajesh N. Dave, Curtis E. Johnson
Abstract
Surface modification of aluminum powders for the purpose of flow improvement was performed and several samples were prepared. Correlations between the flowability and reactivity for these powders as well as for the initial untreated aluminum powder were established. The powders were characterized using Scanning Electron Microscope (SEM), particle size distribution, angle of repose flowability test, Constant Volume Explosion (CVE) combustion test, and Thermo-Gravimetric Analysis (TGA). The surface modification of micron-sized aluminum powders was done by: (1) dry coating nano-particles of silica, titania and carbon black onto the surface of spherical aluminum powders and (2) chemically and physically altering the surface properties of the same powders with methyltrichlorosilane. All surface modifications improved flowability of the powders. CVE measurements indicate that powders with an improved flowability exhibit improved combustion characteristics if the powder treatment does not add an inert component to aluminum. The TGA results do not show significant differences in the reactivity of various powders. Based on combined flowability and CVE characteristics, the silane modified material gave the best results followed by the powders dry coated with carbon, titania and silica, respectively.
Combustion of explosively dispersed Al-Mg-Zr composite particles
March 2020
DOI: https://doi.org/10.1016/j.combustflame.2020.03.012
Journal: Combustion and Flame 217(18):93-102
Demitrios Stamatis, Elliot Wainwright, Shashank Vummidi Lakshman, Michael S Kessler, Tim Weihs
Abstract
Micron-sized composite particles consisting of an Al-Mg alloy and Zr were produced via mechanical milling. Three different particle chemistries were prepared with varying ratios of the Al-Mg alloy to Zr. In addition, the prepared powders were size selected using mechanical sieves. Explosively launched combustion properties of these powders were independently measured as a function of the particle stoichiometry and particle size. Ignition temperatures were measured utilizing a heated filament experiment while combustion efficiency was characterized by measuring the dynamic pressure produced in a closed bomb in which the powder was explosively dispersed under fixed enthalpy conditions. Commercial Al powder, Valimet H-2, was also tested alongside these materials as a benchmark. High-speed video and thermocouple measurements were also obtained for the closed bomb experiments. We observed an increase in combustion efficiency from 30% to 80-90% in the composite materials compared to the pure Al. Furthermore , reaction products were collected and analyzed by powder x-ray diffraction to gain further insight into combustion efficiency and reaction pathways. We observed significant improvement of combustion under these experimental conditions, including higher quasi-static pressures and higher rates of pressure rise, with composite fuels compared to pure Al, even without a secondary oxidizer additive.
Effects of Aluminum Composites on the Regression Rates of Solid Fuels
January 2019
Christian Paravan, Marco Stocco, Simone Penazzo, Juxhin Myzyri, Luigi T. DeLuca and Luciano Galfetti
Abstract
Innovative, mechanically activated Al–polytetrafluoroethylene (PTFE) composites and ammonium perchlorate (AP) coated nano-sized aluminum (C-ALEX) were produced, characterized, and tested as solid fuel additives. The ballistics of fuel formulations based on hydroxylterminated polybutadiene (HTPB) was investigated in a microburner by a time-resolved technique for regression rate ( r f ) data reduction. Both Al-composites show promising results in terms of r f and mass burning rate enhancement. In particular, the C-ALEX showed a percent r f increase over the baseline (HTPB) of 27% at an oxidizer mass flux of 350 kg/(m ² s), without requiring dedicated dispersion procedures. This performance enhancement was nearly constant over the whole investigated range.
Critical Conditions for Ignition of Aluminum Particles in Cylindrical Explosive Charges
January 2006
DOI: 10.1063/1.2263484
Article
David L. Frost, Samuel Goroshin, Jeff Levine, Robert Ripley, and Fan Zhang
Abstract
The critical conditions for the ignition of spherical aluminum particles dispersed during the detonation of long cylindrical explosive charges have been investigated experimentally. The charges consist of packed beds of aluminum particles (Valimet, CA), ranging in size from 3 -115 mum in diameter, and saturated with sensitized liquid nitromethane. The ignition conditions depend on both the charge and particle diameters, which govern the thermal history of the particles as they are dispersed within the conically expanding products. For a given charge diameter, the most reactive particles correspond to an intermediate size (˜55 mum dia). For this particle size, with increasing charge diameter the particle reaction behavior progresses through several distinct regimes: i) no particle reaction, ii) reaction at isolated spots, iii) reaction in distinct radial bands, and iv) continuous reaction of the particle cloud. In each case, a separation between the detonation front and the onset of aluminum reaction is always observed. To determine the point of particle ignition, visible radiation from the charge is recorded, through a slit, with a 3-color pyrometer and with a line spectrometer, with the wavelengths chosen to overlap the AlO emission lines.