A two-phase mixture theory for the deflagration-to-detonation transition (ddt) in reactive granular materials

A Multiphase Godunov Method for Compressible Multifluid and Multiphase Flows

Advances in science and technology of modern energetic materials: an overview.

Metal-based reactive nanomaterials

Metal combustion has received renewed interest largely as a result of the ability to produce and characterize metallic nanoparticles. Much of the highly desirable traits of nanosized metal powders in combustion systems have been attributed to their high specific surface area (high reactivity) and potential ability to store energy in surfaces. In addition, nanosized powders are known to display increased catalytic activity, superparamagnetic behavior, superplasticity, lower melting temperatures, lower sintering temperatures, and higher theoretical densities compared to micron and larger sized materials. The lower melting temperatures can result in lower ignition temperatures of metals. The combustion rates of materials with nanopowders have been observed to increase significantly over similar materials with micron sized particles. A lower limit in size of nanoenergetic metallic powders in some cases may result from the presence of their passivating oxide coating. Consequently, coatings, self-assembled monolayers (SAMs), and the development of composite materials that limit the volume of non-energetic material in the powders have been under development in recent years. After a brief review of the classifications of metal combustion based on thermodynamic considerations and the different types of combustion regimes of metal particles (diffusion vs. kinetic control), an overview of the combustion of aluminum nanoparticles, their applications, and their synthesis and assembly is presented.

Metal particle combustion and nanotechnology

Combustion of nanoaluminum at elevated pressure and temperature behind reflected shock waves

This work presents experimental evidence that the transition from gas-phase diffusion-limited combustion for aluminum particles begins to occur at a particle size of 10 μm at a pressure of 8.5 atm. Measurements of the particle temperature by AlO spectroscopy and three-color pyrometry indicate that the peak temperature surrounding a burning particle approaches the aluminum boiling temperature as particle size is decreased to 10 μm when oxygen is the oxidizer. This reduction indicates that reactions are occurring at or near the particle surface rather than in a detached diffusion flame. When CO 2 is the oxidizer, the combustion temperatures remain near the aluminum boiling temperature for particles as large as 40 μm, indicating that the flame is consistently near the surface throughout this size range. Burn time measurements of 10 and 2.8 μm powders indicate that burn time is roughly proportional to particle diameter to the first power. The burn rates of micron- and nano-particles also show strong pressure dependence. These measurements all indicate that the combustion has deviated from the vapor-phase diffusion limit, and that surface or near-surface processes are beginning to affect the rate of burning. Such processes would have to be included in combustion models in order to accurately predict burning characteristics for aluminum with diameter less than 10 μm.

Evidence for the transition from the diffusion-limit in aluminum particle combustion

: Non-steady burning of solid propellants was investigated both theoretically and experimentally, with attention to combustion instability, transient burning during motor ignition, and extinction by depressurization. The theory is based on a one-dimensional model of the combustion zone consisting of a thin gaseous flame and a solid heat up zone. The non-steady gaseous flame behavior is deduced from experimental steady burning characteristics; the response of the solid phase is described by the time-dependent Fourier equation. Solutions were obtained for dynamic burning rate, flame temperature, and burnt gas entropy under different pressure variations; two methods were employed. First, the equations were linearized and solved by standard techniques. Then, to observe nonlinear effects, solutions were obtained by digital computer for prescribed pressure variations. One significant result is that a propellant with a large heat evolution at the surface is intrinsically unstable under dynamic conditions even though a steady-state solution exists. Another interesting result is that the gas entropy amplitude and phase depend critically on the frequency of pressure oscillation and that either near-isentropic or near-isothermal oscillations may be observable. Experiments with an oscillating combustion chamber and with a special combustor equipped for sudden pressurization tend to support the latter conclusion. (Author)

Nonsteady burning phenomena of solid propellants - theory and experiments

A study of the combustion times for aluminum particles in the size range of 3–11 μm with oxygen, carbon 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 μm, 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 modelers to predict combustion rates of particles in solid rocket motor environments down to particle diameters of a few microns.

A correlation for burn time of aluminum particles in the transition regime

Spatially resolved emission spectra from Bunsen-type flames stabilized in aluminum suspensions in air and oxygen–argon/helium mixtures were obtained using a mechanical-optical scanning system. A low resolution (1.5 nm) spectrometer was used to acquire the broad spectra over the 350–1000 nm range, and a high-resolution (0.04 nm) instrument was used for observation of AlO molecular bands and non-ionized atomic aluminum. The temperature of condensed phase emitters in the flame was derived using polychromatic fitting of the continuum spectra to Planck’s law. AlO temperature was found by fitting of the theoretically calculated shape of the band to experimental data. Peak temperatures of the condensed emitters were found to be approximately 3250 K in aluminum-air flames and approximately 3350 K for oxygen–argon/helium flames. Temperatures derived from AlO spectra coincide with the temperature of the condensed emitters with measurement accuracy and are only 100–200 °C lower than the computed equilibrium flame temperatures. The radial distribution of the temperature profile of the continuous emitters was found via Abel deconvolution and recovered the double-front structure of the Bunsen flame cone, with the outer flame being attributed to a diffusion flame of the fuel-rich products with ambient air. The observation of atomic aluminum lines seen in emission from the outer flame edge and partial self-absorption from the inner flame confirms the structure associated with the double-front structure. The implications of these results for the regime of particle combustion in a dust flame are discussed.

Herman Krier

Papers

Combustion of nanoaluminum at elevated pressure and temperature behind reflected shock waves

Evidence for the transition from the diffusion-limit in aluminum particle combustion

Nonsteady burning phenomena of solid propellants - theory and experiments

A correlation for burn time of aluminum particles in the transition regime

Emission spectroscopy of flame fronts in aluminum suspensions