Flame structure of HMX/GAP propellant at high pressure

The chemical and thermal structure of a HMX/GAP propellant flame was investigated at a pressure of 0.5 MPa using molecular beam mass spectrometry and a microthermocouple technique. The pressure dependence of the burning rate was measured in the pressure range of 0.5–2 MPa. The mass spectrometric probing technique developed for flames of energetic materials was updated to study the chemical structure of HMX/GAP flames at high pressures. Eleven species, including HMX vapor, were identified, and their concentrations were measured in a zone adjacent to the burning surface at pressures of 0.5 and 1 MPa. Temperature profiles in the propellant combustion wave were measured at pressures of 0.5 and 1 MPa. Species concentration profiles were measured at 0.5 MPa. Two main zones of chemical reactions in the flame were found. The data obtained can be used to develop and validate combustion models for HMX/GAP propellants.     

Ammonium Nitrate as an Eco–Friendly Oxidizer for Composite Solid Propellants: Promises and Challenges

Ammonium nitrate (AN) has received attraction globally not only as a nitrogenous fertilizer but also as an oxidizer in gas generators and propellants. Nowadays, great attention is being focused on the development of composite solid propellants with green oxidizers in realizing eco–friendly combustion products. The ammonium perchlorate (AP), which is the work horse oxidizer in composite propellant, needs replacement due to its environmental and human health issues. In this context, AN is regarded as an alternative to AP because of its easy availability and environmentally friendly chlorine free combustion products. However, AN has its own inherent drawbacks such as hygroscopicity, room temperature phase transition, and low burning rate. Recently, several studies have been focused on its phase stabilization and burning rate modification so as to develop solid propellants with improved properties. The knowledge of thermal characteristics of AN is a crucial factor for its applications in propellants and gas generators. This article details the different aspects of polymorphism, phase stabilization, thermal decomposition, hygroscopicity, specific impulse, and burn rate modification of AN and also addresses ways to overcome the inherent weakness of AN as a propellant oxidizer in formulating an effective propellant composition.     

Additive manufacturing of ammonium perchlorate composite propellant with high solids loadings

The effective solid propellant burning rate in a rocket depends on surface area and propellant composition. Currently, the surface area geometry in a rocket is limited to what can be practically cast using molds, etc. Additive manufacturing (AM) could allow the production of unique propellant grain geometries, however printing propellants with high solids loadings and viscosities is not readily possible using currently available printers. A new AM direct write system developed recently in our laboratory, is capable of printing visibly low-void propellants with high end mix viscosities into highly resolved geometries. The system was used to print ammonium perchlorate (AP) composite propellants at 85% solids loading using hydroxyl-terminated polybutadiene (HTPB) and a UV-curable polyurethane binder. The change in HTPB propellant viscosity with time after mixing was measured and the microstructure of the strands was evaluated with X-ray tomography scans. The burning rate of printed and cast strands was measured to compare the quality of the strands at high pressure, since propellants with significant voids should catastrophically fail due to flame spreading. The printed samples burned in a planar fashion up to pressures of 10.34 MPa with consistent rates that were comparable to the cast propellants. The HTPB propellant used was not optimized and showed some porosity due to gas generation, but strands printed with the UV binder exhibited extremely low porosity. A strand printed with no gaps in one half and gaps in the other failed catastrophically where intended at high pressure, demonstrating the ability to spatially grade propellants. This new system can produce adequate strands of composite propellant with high solids loadings without the addition of solvents, special binders (low viscosity, thermal softening, etc.), or restricting use to formulations with lower viscosities, and enables the fabrication of complex propellant grain geometries.     

A numerical study of periodic sandwich propellants with oxygenated binders

We examine sandwich propellants constructed from sheets of pure ammonium perchlorate (AP) interleaved with an AP/binder blend, and construct solutions numerically using a code that fully couples gas-phase and solid-phase processes via an unsteady moving interface. This code has been used elsewhere to simulate the burning of random packs of spherical AP particles embedded in binder. We show that for a stoichiometric configuration, variations of the burning rate with α (a measure of the oxygenation of the AP/binder blend) are not monotonic, but display a weak maximum; and variations of the burning rate with sandwich thickness are monotonic for small α, but display a minimum for large α (e.g. α?=?0.5). When the equivalence ratio is varied, the burning rate displays a maximum on the fuel-lean side when α is small, on the fuel-rich side when α is large. These results, and the manner in which the sandwich topography varies with the different parameters, suggest that the configuration could be invaluable for validating the model ingredients and parameter values of heterogeneous propellant combustion codes.     

The three-dimensional numerical simulation of aluminized composite solid propellant combustion

A three-dimensional numerical framework is presented that examines the burning of aluminized solid propellants. The numerical solver accounts for heat conduction in the solid, combustion in the gas phase, and coupling of these by means of a level set method. The aluminium particles are treated as heat conducting solid spheres. The aluminium particle detachment process is modelled using level sets, but once the particle becomes free from the surface, its subsequent motion in the gas phase is governed by particle dynamics. Some preliminary calculations of the three-dimensional combustion field supported by a pack with embedded aluminium particles are presented.     

Comparison of simplified models for nitramine propellant combustion

Although 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are very similar molecularly and their burning rates as a function of pressure are nearly identical, it is well known that they differ significantly in temperature sensitivity, especially at low pressures. To understand these differences better, three simple models were applied to HMX and RDX combustion. Both the Denison–Baum–Williams and Li–Williams–Margolis models have previously been calibrated for use with RDX. However, the RDX calibration of the Ward–Son–Brewster model was developed in the present work. All three models were compared with relevant measured data including: burning rate, flame stand-off/thickness, combustion stability, and temperature sensitivity. It was shown that all models are capable of accurately determining the burning rate of HMX and RDX as a function of pressure at the baseline initial temperature, but only two of the models are capable of capturing the variation in temperature sensitivity for both HMX and RDX, and only one model can replicate all the other measured characteristics within experimental uncertainty. Analysis using this model suggests that the surface reaction of RDX is much less exothermic than HMX and that there is a shifting between the gas phase and surface reaction dominance with pressure for HMX. This explains why the temperature sensitivity for RDX is nearly flat for low pressures while the temperature sensitivity for HMX increases significantly as the pressure decreases. Importantly, these trends are achieved without adding significant model complexity or having parameters change with pressure or initial temperature.     

Burning rate of homogeneous energetic materials with thermal expansion and varying thermal properties in the condensed phase

We present a study of the one-dimensional flame structure of combusting solid propellants that focuses on the effects of thermal expansion and variable thermal properties in the condensed phase. A nonlinear heat equation is derived for a burning thermo-elastic solid with temperature-dependent specific heat, thermal expansion, and thermal conductivity coefficients. It is solved for different modelling approximations both analytically and numerically. Explicit expressions are derived for the regression rate of the propellant surface as functions of surface temperature and thermal expansion parameters. A simple one-step reaction model of the gas phase is used to study the full structure of propellent flame and illuminate the influence of temperature-dependent material properties on the regression rate, surface temperature, and flame stand-off distance. Results are displayed for HMX and compared with experimental data and numerical simulation with fair success.     

Using level sets for creating virtual random packs of non-spherical convex shapes

Random packs of spheres have been used to model heterogeneous and porous material morphologies during simulations of physical processes such as burning of coal char, convective burning in porous explosives, and regression of solid rocket propellant. Sphere packs have also been used to predict thermo-mechanical properties, permeability, packing density, and dissolution characteristics of various materials. In this work, we have extended the Lubachevsky–Stillinger (LS) sphere packing algorithm to create polydisperse packs of non-spherical shapes for modeling heterogeneity in complex energetic materials such as HMX and pressed gun propellants. In the method, we represent the various particle shapes using level sets. The LS framework requires estimates of inter-particle collision times, and we predict these times by numerically solving a minimization problem. We have obtained results for dense random packs of various convex shapes such as cylinders, spherocylinders, and polyhedra, and we show results with these various particles packed together in a single pack to high packing fraction.     

The numerical simulation of two-dimensional aluminized composite solid propellent combustion

A numerical framework is presented which examines, for the first time, the burning of two-dimensional aluminized solid propellants. Aluminized composite propellants present a difficult mathematical and numerical challenge because of complex physics and topological changes that occur at the propellant surface. For example, both mathematical models and appropriate numerical solvers must describe the regressing burning surface, aluminium particle detachment and evolution throughout the gas-phase flow field, surface tension effects, ignition and combustion of aluminium particles, phase change effects, agglomeration of aluminium particles, radiation feedback to the propellant surface, to name a few. All of these effects must be modelled in a consistent manner. A numerical framework for which these effects can be included in a rational fashion is currently being developed. This framework includes the level set method to capture the solid–gas interface as well as particle motion in the gas phase. Some preliminary calculations of the two-dimensional combustion field supported by a disc pack with embedded aluminium particles are presented.     

Gasless combustion wave with extremely high excess enthalpy under heat loss conditions

A numerical experiment on investigation of a gasless combustion wave propagating at the limit due to a high excess enthalpy in the heating zone is performed. Under heat loss conditions, waves emerge on the surface of the combustion front, causing changes in the rate of chemical reactions similar to those realized on the burning surface of propellants and explosives.     

Modeling of HMX combustion

A mechanism of HMX combustion was proposed and the corresponding model was developed under the assumption that the combustion wave consists of two zones, with consideration given to the reaction of decomposition and vaporization of the initial energetic material in the condensed phase and the subsequent decomposition of its vapor in the gas phase. An analysis of the results showed that, at low pressures, the burning rate is largely determined by the exothermic decomposition of the material in the condensed phase, but at pressure above ∼20 atm, the processes in the gas phase begin to play an increasingly important role, where the limiting process is the bimolecular activation reaction with the subsequent dissociation of HMX accompanied by the secondary reactions between the products. A comparison of the calculation results with experimental data showed that the model adequately describes a number of characteristics of the combustion wave and ballistic properties, such as the burning rate and its sensitivity to pressure and initial temperature.     

Flame structure and combustion chemistry of energetic materials

A review of experimental studies of the structure of the flame of a number of energetic materials (EMs), such as ammonium perchlorate, ammonium dinitramide, RDX, HMX, and some model composite propellants on their bases, is presented. Experimental techniques for studying the flame structure of EMs, probe mass spectrometry and the thermocouple method, are described. An analysis of experimental data on the flame structure and combustion chemistry and a comparison of them with simulations within the framework of modern mechanisms of chemical reactions in EM flames are performed.     

On the structure of the combustion wave of nitroglycerine-based propellants

The parameters of the temperature distribution in the combustion wave of nitroglycerin-based propellants N and NB are analyzed and compared. The aim of the study is to explain the known experimental fact that the size of hotspots and the critical quenching diameter for propellant NB (more rapidly burning) are larger than those for propellant N. It is demonstrated that, at a given burning rate, the burning surface temperature, heat conduction zone thickness, temperature gradient near the burning surface, and the dark zone temperature for propellants N and NB are the same, but the fizz zone thickness for NB is approximately twice as wide as that for N. The dependence of the ratio of the hotspot size to the fizz zone thickness is described by a single power law for both propellants. It is also shown that the hotspot size can be defined as the distance between two consecutive transverse waves, which, in turn, is determined by the delay in the initiation of each following wave.     

Quench collection of nano-aluminium agglomerates from combustion of sandwiches and propellants

An experimental investigation has been carried out to measure the size of nano-aluminium agglomerates emerging from the combustion of nano-aluminized sandwiches and composite solid propellants. Nano-aluminium of median size of 50 nm produced in-house by the electrical wire explosion method is used in these samples. Propellants with different sizes of coarse and fine ammonium perchlorate are considered. Surface features of sandwiches and a propellant whose burning was interrupted by rapid depressurization are examined in a scanning electron microscope. The combustion products of the sandwiches and propellants are quenched close to the burning surface and collected in a quench collection set-up. The surface features of rapid-depressurization quenched sandwiches exhibit relatively large nano-aluminium clusters—of the order a few micrometres—particularly in the binder lamina. Quench-collected nano-aluminium exhibits significant agglomeration, but only a small fraction of the agglomerates are in the 1–3 μm range, except for both the coarse and fine AP particles used in the formulation being large, but even there they do not exceed ∼5 μm in size. This is expected to be benign for reduced smoke propellant applications from exhaust signature point of view, and to decrease the specific impulse losses without sacrificing the energetics of the propellant.     

Experimental data and model predictions of aluminium agglomeration in ammonium perchlorate-based composite propellants including plateau-burning formulations

Sixteen propellant formulations based on ammonium perchlorate (AP), hydroxyl-terminated polybutadiene, and aluminium particles have been tested for size distribution of aluminium agglomerates emerging from their burning surface. The formulations are based on a bimodal size distribution of AP particles. Ten of the formulations exhibit one or two plateaus/mesa in their burning rate variation with pressure (zero/negative pressure exponent of burning rate). The relevant formulation variables, namely, coarse and fine AP sizes and coarse-to-fine ratio, aluminium size and content, and two different curing agents, have been varied. Tests are performed in the 1–10 MPa pressure range. A direct correlation between burning rate and agglomerate size exists for propellants with normal burning rate trends but a neutral or inverse correlation is observed for those exhibiting plateau burning behaviour. Larger the parent aluminium size, lesser the agglomeration, as expected; but the effect of aluminium content is non-monotonic. The coarse AP size influences the aluminium agglomerate size as expected from the pocket model regardless of plateau burning effects. The agglomerate size decreases with increase in fine AP size, however. A computer model developed earlier at this laboratory for prediction of aluminium agglomerates based on three-dimensional packing of particles and deduction of AP particles with attached leading edge diffusion flames is applied to the present formulations. The model under-predicts the agglomerate size, only marginally for propellants that do not exhibit plateau burning rate trends, but substantially, otherwise. This is because it does not take into account effects of binder melt flow and is independent of the curing agent of the binder.     

Holographic Observation of AluminumAgglomerates near Surface Area of SolidRocket Propellants during Burning Process

l.IntroductionMetalaluminumisusual1yaddedtosolidrocketpropellantstoincreasethrustandspecificimpu1se.Inaddition,a1uminumoxideparticlesproducedinhightemPeratureburningareacaninturnsuppresshighfrequencycombustioninstabilities.Fromthetheo-reticalcombustionmode1ofsolidproPellants['2j,oxiderandbinder,maincompositionofsolidproPellants,arefirstdecomPOsedandvaPOrizcdintheburningprocere,sothatthealuminumparticlesareexposedonthesurfaceofsolidproPCllants.SomeoftheexPOsedaluminumparticlesescaPerapedl…     

Catalytic effect of bis(carbollyl) complexes of metals on the combustion of condensed systems

The mechanism of the catalytic action of bis(dicarbollyl) complexes of metals on the combustion of composite, pyroxylin, and double-base propellants was studied. The main factors controlling the efficiency of catalysts of this type were identified. It was established that the significant catalytic effect of bis(dicarbollyl) complexes of metals on combustion is associated with the thermal decomposition of the catalyst in the high-temperature zone of the gas phase for composite propellants, with the burning surface temperature for pyroxylin propellants, and with a change in the effective activation energy for double-base propellants. The experimental and calculation results were found to be in satisfactory agreement.     

Numerical model of two-dimensional heterogeneous combustion in porous media under natural convection or forced filtration

A novel mathematical model and original numerical method for investigating the two-dimensional waves of heterogeneous combustion in porous media are proposed and described in detail. The mathematical model is constructed within the framework of the model of interacting interpenetrating continua and includes equations of state, continuity, momentum conservation and energy for solid and gas phases. Combustion, considered in the paper, is due to the exothermic reaction between fuel in the porous solid medium and oxidiser contained in the gas flowing through the porous object. The original numerical method is based on a combination of explicit and implicit finite-difference schemes. A distinctive feature of the proposed model is that the gas velocity at the open boundaries (inlet and outlet) of the porous object is unknown and has to be found from the solution of the problem, i.e. the flow rate of the gas regulates itself. This approach allows processes to be modelled not only under forced filtration, but also under free convection, when there is no forced gas input in porous objects, which is typical for many natural or anthropogenic disasters (burning of peatlands, coal dumps, landfills, grain elevators). Some two-dimensional time-dependent problems of heterogeneous combustion in porous objects have been solved using the proposed numerical method. It is shown that two-dimensional waves of heterogeneous combustion in porous media can propagate in two modes with different characteristics, as in the case of one-dimensional combustion, but the combustion front can move in a complex manner, and gas dynamics within the porous objects can be complicated. When natural convection takes place, self-sustaining combustion waves can go through the all parts of the object regardless of where an ignition zone was located, so the all combustible material in each part of the object is burned out, in contrast to forced filtration.     

Nonideal regimes of deflagration and detonation of black powder

The explosive and deflagration properties of black powder differ significantly from those of modern propellants and compositions based on ammonium nitrate or ammonium perchlorate. Possessing a high combustibility, black powder is capable of maintaining stable combustion at high velocities in various shells, be it steel shells or thin-walled plastic tubes, without experiencing deflagration-to-detonation transition. It is extremely difficult to detonate black powder, even using a powerful booster detonator. The results of numerical simulations of a number of key experiments on the convective combustion and shock initiation of black powder described in the literature are presented. The calculations were performed within the framework of a model developed previously for describing the convective combustion of granulated pyroxylin powders, with small modifications being introduced to allow for the specific properties of black powder. The thermophysical properties of the products of combustion and detonation and the parameters of the equation of state of black powder were determined from thermodynamic calculations. The calculation results were found to be in close agreement with the experimental data. The simulation results were used to analyze the regularities of the wave processes in the system and their relation to the properties of black powder and the experimental conditions. It was demonstrated that the effects observed could be explained by a weak dependence of the burning rate of black powder on the pressure.     

Improved method of measuring pressure coupled response for composite solid propellants

Pressure coupled response is one of the main causes of combustion instability in the solid rocket motor. It is also a characteristic parameter for predicting the stability. The pressure coupled response function is usually measured by different methods to evaluate the performance of new propellant. Based on T-burner and “burning surface doubled and secondary attenuation”, an improved method for measuring the pressure coupled response of composite propellant is introduced in this article. A computational fluid dynamics (CFD) study has also been conducted to validate the method and to understand the pressure oscillation phenomenon in T-burner. Three rounds of tests were carried out on the same batch of aluminized AP/HTPB composite solid propellant. The experimental results show that the sample propellant had a high response function under the conditions of high pressure (~11.5 MPa) and low frequency (~140 Hz). The numerically predicted oscillation frequency and amplitude are consistent with the experimental results. One practical solid rocket motor using this sample propellant was found to experience pressure oscillation at the end of burning. This confirms that the sample propellant is prone to combustion instability. Finally, acoustic pressure distribution and phase difference in T-burner were analyzed. Both the experimental and numerical results are found to be associated with similar acoustic pressure distribution. And the phase difference analysis showed that the pressure oscillations at the head end of the T-burner are 180° out of phase from those in the aft end of the T-burner.