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Composite solid propellants surface structure and profile characteristics burning with various oxidizers and polyurethane binder by scanning electron microscopy
During the launch of the Space Shuttle vehicle, the burning of liquid hydrogen fuel with liquid oxygen at extreme high temperatures inside the three space shuttle main engines, and the burning of the solid propellant mixture of ammonium perchlorate oxidizer, aluminum fuel, iron oxide catalyst, polymer binder, and epoxy curing agent in the two solid rocket boosters result in the formation of a large cloud of hot, buoyant toxic exhaust gases near the ground level which subsequently rises and entrains into ambient air until the temperature and density of the cloud reaches an approximate equilibrium with ambient conditions. In this paper, toxic gas dispersion for various gases are simulated over the web for varying environmental conditions which is provided by rawinsonde data. The model simulates chemical concentration at ground level up to 10 miles (1 KM grids) in downrange up to an hour after launch. The ambient concentration of the gas dispersion and the deposition of toxic particles are used as inputs for a human health risk assessment model. The advantage of the present model is the accessibility and dissemination of model results to other NASA centers over the web. The model can be remotely operated and various scenarios can be analyzed.
Large rocket motors may violently explode when exposed to accidental fires. Even hot metal fragments from a nearby accident may penetrate the propellant and ultimately cause thermal ignition. A mechanistic understanding of heated propellants leading to thermal runaway is a major unsolved problem. Here we show that thermal ignition in propellants can be predicted using a universal cookoff model coupled to a micromechanics pressurization model. Our model predicts the time to thermal ignition in cookoff experiments with variable headspace volumes. Furthermore, we found that experiments with headspace volumes are more prone to deformation which distorts pores and causes increased permeability when the propellant expands into this headspace. Delayed ignition with larger headspace volume correlates with lower headspace pressures during decomposition. We found that our predictions matched experimental measurements best when the initial propellant was impermeable to gas flow rather than being permeable. Similar behavior is expected with other energetic materials with rubbery binders. Our model is validated using data from a separate laboratory. We also present an uncertainty analysis using Latin Hypercube Sampling (LHS) of thermal ignition caused by a steel fragment embedded in the propellant.
In polymer-filled granular composites, damage may develop in mechanical loading prior to material failure. Damage mechanisms such as microcracking or plastic deformation in the binder phase can substantially alter the material’s mesostructure. For energetic materials, such as solid propellants and plastic bonded explosives, these mesostructural changes can have far reaching effects including degraded mechanical properties, potentially increased sensitivity to further insults, and changes in expected performance. Unfortunately, predicting damage is nontrivial due to the complex nature of these composites and the entangled interactions between inelastic mechanisms. In this work, we assess the current literature of experimental knowledge, focusing on the pressure-dependent shear response, and propose a simple simulation framework of bonded particles to study four limiting-case material formulations at both meso- and macro-scales. Further, to construct the four cases, we systematically vary the relative interfacial strength between the polymer binder and granular filler phase and also vary the polymer’s glass transition temperature relative to operating temperature which determines how much the binder can plastically deform. These simulations identify key trends in global mechanical response, such as the emergence of strain hardening or softening regimes with increasing pressure which qualitatively resemble experimental results. By quantifying the activation of different inelastic mechanisms, such as bonds breaking and plastically straining, we identify when each mechanism becomes relevant and provide insight into potential origins for changes in mechanical responses. The locations of broken bonds are also used to define larger, mesoscopic cracks to test various metrics of damage. We primarily focus on triaxial compression, but also test the opposite case of triaxial extension to highlight the impact of Lode angle on mechanical behavior.
Fast burning rates in thin film solid composite propellants composed of McCormick-Selph 510, 164 monopropellant, oxidizer and polyvinyl chloride binder
The current experimental program was designed to systematically investigate the role of the oxidizer in the thermal degradation process of composite propellants. The scanning electron microscope (SEM) was used to examine the failure sites in thermally degraded propellant samples. The formulation variables tested were oxidizer purity, oxidizer particle size, and oxidizer to binder bonding agent. The binder, a saturated hydrocarbon, was kept constant throughout the experiments. The oxidizers were: AP, chlorate-doped AP, arsenate-doped AP, and phosphate-doped AP. The oxidizer particle size distribution was 60% of the large fraction and 40% of the small fraction. The bonding agent, when present, was used at the 0.15% level. The data showed that both the oxidizer purity and particle size had an important affect on the thermal degradation process. The affect of the oxidizer particle size was more noticeable at the higher temperature and stress levels. An examination of the failure site, by SEM, of propellants subject to these latter conditions indicated that the fracturing of the large oxidizer particles led to the propellant cracking.
This paper presents a model for the purpose of estimating the fraction of aluminum powder that will form agglomerates at the surface of deflagrating composite propellants. The basic idea is that the fraction agglomerated depends upon the amount of aluminum that melts within effective binder pocket volumes framed by oxidizer particles. The effective pocket depends upon the ability of ammonium perchlorate modals to encapsulate the aluminum and provide a local temperature sufficient to ignite the aluminum. Model results are discussed in the light of data showing effects of propellant formulation variables and pressure.
The results of research aimed at improving the predictability of internal ballistics performance of solid-propellant rocket motors (SRM's) including thrust imbalance between two SRM's firing in parallel are presented. Static test data from the first six Space Shuttle SRM's is analyzed using a computer program previously developed for this purpose. The program permits intentional minor design biases affecting the imbalance between any two SMR's to be removed. Results for the last four of the six SRM's, with only the propellant bulk temperature as a non-random variable, are generally within limits predicted by theory. Extended studies of internal ballistic performance of single SRM's are presented based on an earlier developed mathematical model which includes an assessment of grain deformation. The erosive burning rate law used in the model is upgraded and made more general. Excellent results are obtained in predictions of the performances of five different SRM's of quite different sizes and configurations. These SRM's all employ PBAN type propellants with ammonium perchlorate oxidizer and 16 to 20% aluminum except one which uses carboxyl terminated butadiene binder. The only non-calculated parameters in the burning rate equations that are changed for the different SRM's are the zero crossflow velocity burning rate coefficients and exponents. The results, in general, confirm the importance of grain deformation. The improved internal ballistic model makes practical development of an effective computer program for application of an optimization technique to SRM design which is also demonstrated. The program uses a pattern search technique to minimize the difference between a desired thrust-time trace and one calculated based on the internal ballistic model.
A high performance propellant having greatly reduced hydrogen chloride emission is presented. It is comprised of: (1) a minor amount of hydrocarbon binder (10-15%), (2) at least 85% solids including ammonium nitrate as the primary oxidizer (about 40% to 70%), (3) a significant amount (5-25%) powdered metal fuel, such as aluminum, (4) a small amount (5-25%) of ammonium perchlorate as a supplementary oxidizer, and (5) optionally a small amount (0-20%) of a nitramine.
A transient combustion model of nitramine propellants is combined with an isentropic compression shock formation model to determine the role of nitramine propellant combustion in DDT, excluding effects associated with propellant structural properties or mechanical behavior. The model is derived to represent the closed pipe experiment that is widely used to characterize explosives, except that the combustible material is a monolithic charge rather than compressed powder. Computations reveal that the transient combustion process cannot by itself produce DDT by this model. Compressibility of the solid at high pressure is the key factor limiting pressure buildups created by the combustion. On the other hand, combustion mechanisms which promote pressure buildups are identified and related to propellant formulation variables. Additional combustion instability data for nitramine propellants are presented. Although measured combustion response continues to be low, more data are required to distinguish HMX and active binder component contributions. A design for a closed vessel apparatus for experimental studies of high pressure combustion is discussed.
Low modulus solid propellants family for low thrust-to-mass ratio fully case bonded end-burning motors, using polymer network theory for binder formulation
An advanced lightweight insulation system suitable for use in long duration, low pressure planetary orbiter-type motor applications was developed. Experiments included the screening of various filler and binder materials with optimization studies combining the best of each. Small scale test motor data were used to judge the degree of success.
Several studies are described of the chemistry of solid propellant combustion which employed a fast-scanning optical spectrometer. Expanded abstracts are presented for four of the studies which were previously reported. One study of the ignition of composite propellants yielded data which suggested early ammonium perchlorate decomposition and reaction. The results of a study of the spatial distribution of molecular species in flames from uncatalyzed and copper or lead catalyzed double-based propellants support previously published conclusions concerning the site of action of these metal catalysts. A study of the ammonium-perchlorate-polymeric-fuel-binder reaction in thin films, made by use of infrared absorption spectrometry, yielded a characterization of a rapid condensed-phase reaction which is likely important during the ignition transient and the burning process.
A mathematical model is developed to predict burn rate augmentation due to strain in a composite solid propellant. The model assumes the effect is due to the ability of the flame to penetrate the small fissures and voids that form when a propellant is strained. The number and size of these fissures is obtained by applying a flaw propagation analysis to randomly distributed flaws that form when the binder-oxidizer particle bonds break under stress. A flame height is calculated with Summerfield's burn rate equation and is used to compute the burn rate augmentation based upon the additional burn area created when the flame penetrates the fissures. Comparisons are made with data obtained from published sources. The existence of threshold pressure and strains, above which augmentation occurs, is verified although the model predicts a lower threshold pressure and higher threshold strain than expected. Further results and applications of the model are discussed.
Over a pressure range of 3.5-7 MPa and a frequency range of 500-2000 Hz and compared to propellants having equivalent energy and burn rate, HMX produces less pressure-coupled acoustic driving than AP and is equivalent to NC/TMETN. Formation of carbonaceous combustion products indicates that binder decomposition does not follow equilibrium thermochemistry, and that this is aggravated by fuel richness or the absence of AP.
A computerized mathematical model of the combustion response function of composite solid propellants was developed with particular attention to the contributions of the solid phase heterogeneity. The one-dimensional model treats the solid phase as alternating layers of ammonium perchlorate and binder, with an exothermic melt layer at the surface. Solution of the Fourier heat equation in the solid provides temperature and heat flux distributions with space and time. The problem is solved by conserving the heat flux at the surface from that produced by a suitable model of the gas phase. An approximation of the BDP flame model is utilized to represent the gas phase. By the use of several reasonable assumptions, it is found that a significant portion of the problem can be solved in closed form. A method is presented by which the model can be applied to tetramodal particle size distributions. A computerized steady-state version of the model was completed, which served to validate the various approximations and lay a foundation for the combustion response modeling. The combustion response modeling was completed in a form which does not require an iterative solution, and some preliminary results were acquired.
The current paper presents results from a combined research effort by Louisiana Tech University (LTU) and NASA Stennis Space Center (SSC) to develop a new alumina-silicate based cementitious binder capable of acting as a high performance refractory material with low heat ablation rate and high early mechanical strength. Such a binder would represent a significant contribution to NASA's efforts to develop a new generation of refractory 'hot face' liners for liquid or solid rocket plume environments. This project was developed as a continuation of on-going collaborations between LTU and SSC, where test sections of a formulation of high temperature geopolymer binder were cast in the floor and walls of Test Stand E-1 Cell 3, an active rocket engine test stand flame trench. Additionally, geopolymer concrete panels were tested using the NASA-SSC Diagnostic Test Facility (DTF) thruster, where supersonic plume environments were generated on a 1ft wide x 2ft long x 6 inch deep refractory panel. The DTF operates on LOX/GH2 propellants producing a nominal thrust of 1,200 lbf and the combustion chamber conditions are Pc=625psig, O/F=6.0. Data collected included high speed video of plume/panel area and surface profiles (depth) of the test panels measured on a 1-inch by 1-inch giving localized erosion rates during the test. Louisiana Tech conducted a microstructure analysis of the geopolymer binder after the testing program to identify phase changes in the material.
Report presents theoretical study of dewetting between elastomeric binder and filler particles of highly filled elastomer under multiaxial tension and resulting dilatation of elastomer. Study directed toward understanding and predicting nonlinear stress-vs.-strain behavior of filled elastomeric rocket propellant, also applicable to rubber in highly loaded tire or in damping pad.