Composite propellants are composed of a solid oxidizer that is mixed into a hydrocarbon binder that when polymerized results in a solid mass capable of selfsustained combustion after ignition. Plateau propellants exhibit burning rate curves that do not follow the typical linear relationship between burning rate and pressure when plotted on a log-log scale, and because of this deviation their burning behavior is classified as anomalous burning. It is not unusual for solid-particle additives to be added to propellants in order to enhance burning rate or other properties. However, the effect of nano-size solid additives in these propellants is not fully understood or agreed upon within the research community. The current project set out to explore what possible variables were creating this result and to explore new additives. This thesis contains a literature review chronicling the last half-century of research to better understand the mechanisms that govern anomalous burning and to shed light on current research into plateau and related propellants. In addition to the review, a series of experiments investigating the use of nanoscale TiO2-based additives in AP-HTPB composite propellants was performed. The baseline propellant consisted of either 70% or 80% monomodal AP (223 μm) and 30% or 20% binder composed of IPDI-cured HTPB with Tepanol. Propellants’ burning rates were tested using a strand bomb between 500 and 2500 psi (34.0-170.1 atm). Analysis of the burning rate data shows that the crystal phase and synthesis method of the TiO2 additive are influential to plateau tailoring and to the apparent effectiveness of the additive in altering the burning rate of the composite propellant. Some of the discrepancy in the literature regarding the effectiveness of TiO2 as a tailoring additive may be due to differences in how the additive was produced. Doping the TiO2 with small amounts of metallic elements (Al, Fe, or Gd) showed additional effects on the burning rate that depend on the doping material and the amount of the dopant.

Presented in this thesis is a study of the effects of nano-sized particles used as a catalytic additive in composite solid propellant. This study was done with titanium oxide (titania)-based particles, but much of the findings and theory are applicable to any metal oxide produced by a similar method. The process required for efficiently producing larger batches of nanoparticle additives was seen to have a significant impact on the effectiveness of the additive to modify the burning rate of composite propellant consisting of ammonium perchlorate (AP) and hydroxyl terminated polybutadiene (HTPB). Specifically, titania was seen to be both an effective and ineffective burning rate modifier depending on how the nanoparticle additive was dried and subsequently heat treated. Nanoadditives were produced by various synthesis methods and tested in composite propellant consisting of 80 percent AP. Processability and scale-up effects are examined in selecting ideal synthesis methods of nanoscale titanium oxide for use as a burning rate modifier in composite propellant. Sintering of spray-dried additive agglomerates during the heat-treating process was shown to make the agglomerates difficult to break up during mixing and hinder the dispersion of the additive in the propellant. A link between additive processing, agglomerate dispersion mechanics and ultimately catalytic effect on the burning rate of AP/HTPB propellants has been developed by the theories presented in this thesis. This thesis studies the interaction between additive dispersion and the dispersion of reactions created by using fine AP in multimodal propellants. A limit in dispersion with powder additives was seen to cause the titania catalyst to be less effective in propellants containing fine AP. A new method for incorporating metal oxide nanoadditives into composite propellant with very high dispersion by suspending the additive material in the propellant binder is introduced. This new method has produced increases in burning rate of 50 to 60 percent over baseline propellants. This thesis reviews these studies with a particular focus on the application and scale-up of these nanoparticle additives to implement these additives in actual motor propellants and assesses many of the current problems and difficulties that hinder the nanoadditives’ true potential in composite propellant.

This thesis examines the effects of nanoparticle, metal-oxide additives on the burning rate of composite solid propellants. Recent advancements in chemical synthesis techniques have allowed for the production of improved solid rocket propellant nano-scale additives. These additives show larger burning rate increases in composite propellants compared to previous additive generations. In addition to improving additive effectiveness, novel synthesis methods can improve manufacturability, reduce safety risks, and maximize energy efficiency of nano-scale burning rate enhancers. Several different nano-sized additives, each titania-based, were tested and compared for the same baseline AP/HTPB formulas and AP size distributions. The various methods demonstrate the evolution in our methods from spray-dried powders to pre-mixing the additive in the HTPB binder, and finally to a method of producing the additive directly in the binder as a nano-assembly. Burning rate increases as high as 80% at additive mass loadings of less than 0.5% were seen in non-aluminized, ammonium perchlorate-based propellants over the pressure spectrum of 500 psi (3.5 MPa) to 2250 psi (15.5 MPa). Increases in burning rate up to 73% were seen in similarly formulated aluminized propellants. During the past several years, the research team has refined laboratory-scale techniques for quickly and reliably assessing the mixing and performance of composite propellants with catalytic nanoparticle additives. This thesis also documents some of the details related to repeatability, accuracy, and realism of the methods used in the team’s recent nano-additive research; it also introduces the latest techniques for producing propellants with nano-sized additives and provides new burning rate results for the entire scope of additives and mixing methods. Details on the propellant characterization methods with regard to physical and combustion properties are provided. Snapshots from atmospheric propellant combustion videos taken with a Photron FASTCAM SA3 high-speed camera are included along with existing pressure and light-emission responses.

<p>The performance of solid rocket motors (SRMs) is extremely dependent on propellant formulation, operating pressure, and initial grain geometry. Traditionally, propellant grains are cast into molds, but it is difficult to remove the grains without damage if the geometry is too complex. Cracks or voids in propellant can lead to erratic burning that can break the grain apart and/or potentially overpressurize the motor. Not only is this dangerous, but the payload could be destroyed or lost. Some geometries (i.e. internal voids or intricate structures) cannot be cast and there is no consistent nor economical way to functionally grade grains made of multiple propellant formulations at fines scales (~ mm) without the risk of delamination between layers or the use of adhesives, which significantly lower performance. If one could manufacture grains in such a way, then one would have more control and flexibility over the design and performance of a SRM. However, new manufacturing techniques are required to enable innovation of new propellant grains and new analysis techniques are necessary to understand the driving forces behind the combustion of non-traditionally manufactured propellant.</p> <p>Additive manufacturing (AM) has been used in many industries to enable rapid prototyping and the construction of complex hierarchal structures. AM of propellant is an emerging research area, but it is still in its infancy since there are some large challenges to overcome. Namely, high performance propellant requires a minimum solids loading in order to combust properly and this translates into mixtures with high viscosities that are difficult to 3D print. In addition, it is important to be able to manufacture realistic propellant formulations into grains that do not deform and can be precisely functionally graded without the presence of defects from the printing process. The research presented in this dissertation identifies the effect of a specific AM process called Vibration Assisted Printing (VAP) on the combustion of propellant, as well as the development of binders that enable UV-curing to improve the final resolution of 3D printed structures. In addition, the combustion dynamics of additively manufactured layered propellant is studied with computational and experimental methods. The work presented in this dissertation lays the foundation for progress in the developing research area of additively manufactured energetic materials. </p> <p>The appendices of this dissertation presents some additional data that could also be useful for researchers. A more detailed description of the methods necessary to support the VAP process, additional viscosity measurements and micro-CT images of propellant, the combustion of Al/PVDF filament in windowed propellant at pressure, and microexplosions of propellant with an Al/Zr additive are all provided in this section. </p>

<div>The new technique of Vibration-Assisted 3D Printing (VAP) offers significant potential for leveraging the geometric flexibility of additive manufacturing (AM) into the realm of solid energetics. The first part of this work compares the print capabilities of a custom-made VAP printer to those of an established commercial direct-write printer using a polymer clay. Characterization tests were conducted and a variety of other shapes were printed comparing the two methods in their turning quality, feature resolution, unsupported overhang angle, negative space feature construction, and less-than-fully-dense self-supported 3D lattices. The porosity and regularity of the printed lattices were characterized using X-ray microtomography (MicroCT) scans. The quality of the shapes was compared using statistical methods and a MATLAB edge-finding code. The results show that the VAP printer can manufacture parts of superior resolution than the commercial printer, due to its ability to extrude highly viscous material through a smaller nozzle diameter. The VAP print speeds were also found to be as high as twenty times higher than those of the direct write printer.</div><div>Following up on this work, a second study explored the possibility of modifying grain geometry through variation of printed infill design using an ammonium perchlorate composite propellant (APCP). In the propellant formulation, a polymer that cures under ultra-violet (UV) light was used instead of the more common hydroxyl-terminated polybutadiene (HTPB). Although this formulation is a less-effective fuel than HTPB, its use enables layer-by-layer curing for improved structural strength during printing. Using VAP, cylindrical propellant charges were prepared using a gyroidal infill design with a range of internal porosities (infill amounts). Some additional propellant grains were prepared with both vertical and concentric layering of different infill amounts. These grains were then burned beginning at atmospheric pressure in a constant-volume Parr cell to measure the resulting pressure output. Analysis of the pressure trace data shows that a less-dense infill increases the maximum pressurization rate, due to the presence of small voids spaced roughly uniformly throughout the grain that increase the burning surface area. We show that additive manufacturing-based propellant grain modification can be used to tailor the pressure-time trace through adjustment of the number and size of small voids. Specifically, this study shows that, using a graded functional geometry, the duration of gas generation can be controlled. This work represents a preliminary effort to explore the possibilities to propellant</div><div>12</div><div>manufacture offered by additive manufacturing and to begin to address the challenges inherent in making it practical.</div>

<p>This work presents the development and/or application of several laser diagnostics for studying the flame structure of composite propellant flames. These studies include examining the flame structure of novel energetic materials with potential as propellant ingredients, the near-surface flame structure of basic composite propellants, and the global flame structure of propellants containing metal additives.<br></p><p><br></p><p>First, the characterization of the deflagration of various novel energetic cocrystals is presented. The synthesis and development of novel energetic materials is a costly and challenging process. Rather than synthesizing new materials, cocrystallization provides the potential opportunity to achieve improved properties of existing energetic materials. This work presents the characterization of the effect of cocrystallization on the deflagration of a 2:1 molar cocrystal of CL-20 and HMX as well as a 1:1 molar cocrystal of CL-20 and TNT. A hydrogen peroxide (HP) solvate of CL-20 as well as a polycrystalline composite of HMX and ammonium perchlorate (AP) were also studied. A physical mixture of each material was also tested for comparison. The burning rate of each material was measured as a function of pressure. Flame structure during self-deflagration was examined using planar laser-induced fluorescence (PLIF) of CN and OH. The burning rate of the HMX/CL-20 cocrystal and the CL-20/HP solvate closely matched that of CL-20, but the burning rate of the TNT/CL-20 cocrystal was between the burning rate of its coformers. All HMX/AP materials had a higher burning rate than either HMX or AP individually and the burning rate of a physical mixture was found to be a function of particle size. The differences in the burning rate of the physical mixtures and composite crystal of HMX/AP can be explained by changes in the flame structure observed using PLIF. Burning rates and flame structure of the cocrystals were found to closely match those of their respective physical mixtures when smaller particle sizes were used (approx. less than 100 um). The results obtained demonstrate that the deflagration behavior of the coformers is not indicative of the deflagration behavior of the resulting physical mixture or cocrystal. However, changes in the resulting flame structure greatly affect the burning rate.</p><p><br></p><p>Next, PLIF of nitric oxide (NO) was utilized to characterize the near surface flame structure of composite propellants of AP and hydroxyl-terminated polybutadiene (HTPB) containing varying particle sizes of AP burning at 1 atm in air. In all propellants, the NO PLIF signal was strongest close to the burning propellant surface and fell to a non-zero constant value within ~1 mm of the surface where it remained throughout the remainder of the flame. Distinct diffusion-flame-like structure was observed above large individual burning AP particles in the propellant containing a bimodal distribution of 400 and 40 um AP. In contrast, the flame of a propellant containing only fine AP (40 um) behaved like a homogeneous, premixed flame. The flame of the propellant containing a bimodal distribution of 200 and 40 um AP also showed similar behavior to a premixed flame with some heterogeneous structure indicating that, at this pressure, the propellant is approaching a limit where the particle sizing is small enough that the flame behaves like a homogeneous, premixed flame. Additionally, propellants containing aluminum were tested. No significant differences were observed in the NO PLIF behavior between the propellants with and without aluminum suggesting that, at these conditions, the aluminum does not have a significant effect on the AP/HTPB flame structure near the burning surface.</p><p><br></p><p>The effect of aluminum particle size on the temperature of aluminized-composite-propellant flames burning at 1 atm is also presented. In this work, 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, AP-HTPB-propellant flames were performed as a function of height above the burning propellant surface. Three aluminized propellants with varying aluminum particle size (nominally 31 um, 4.5 um, or 80 nm) and one non-aluminized AP-HTPB propellant were studied while burning in air at 1 atm. A wavelength-modulation-spectroscopy (WMS) diagnostic was utilized to measure temperature and mole fraction of CO 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.</p><p><br></p><p>The study of the effect of aluminum particle size on the temperature of aluminized, composite-propellant flames was then extended to characterize the same propellants burning at elevated pressures ranging from 1 to 10 atm. A novel mid-infrared scanned-wavelength direct absorption technique was developed to acquire measurements of temperature and CO in particle-laden propellant flames burning at up to 10 atm. The results from the application of this diagnostic are among the very first measurements of gas properties in aluminized composite propellant flames burning at pressures above atmospheric pressure. In all propellants, the flame temperature and combustion efficiency of the propellant flames increased with an increase in pressure. In addition, the propellants with smaller aluminum particle sizes achieved higher flame temperatures as the particles were able to ignite and react faster. However, the propellants containing nano-scale and the smallest micron-scale aluminum powders had similar global flame temperatures suggesting that at some point a decrease in particle size results in minimal gains in the overall flame temperature. The results demonstrate how well measurements of gas properties can be used to understand the behavior of the aluminum particle combustion in the flame.</p><p><br></p><p>Last, the design, development, and application of a laser-absorption-spectroscopy diagnostic capable of providing quantitative, time-resolved measurements of gas temperature and HCl concentration in flames of aluminized, composite propellant flames is presented. This diagnostic utilizes a quantum-well distributed-feedback tunable diode laser emitting near 3.27 um to measure the absorbance spectra of one or two adjacent HCl lines using a scanned-WMS technique which is insensitive to non-absorbing transmission losses caused by metal particulates in the flame. This diagnostic was applied to characterize the spatial and temporal evolution of temperature and/or HCl mole fraction in small-scale flames of AP-HTPB composite propellants containing either an aluminum-lithium alloy or micron-scale aluminum. Experiments were conducted at 1 and 10 atm. At both pressures, the flame temperature of the aluminum-lithium propellant, on a time-averaged basis, was 80 to 200 K higher than that of the aluminum-propellant (depending on location in the flame) indicating more complete combustion. In addition, the mole fraction of HCl in the aluminum-lithium propellant flame reached values 65-70% lower than the conventional aluminum-propellant flame at the highest measurement location in the flame. The measurements at both pressures showed similar trends in the reduction of HCl in the aluminum-lithium propellant flame but at 10 atm this occurred on a length scale an order of magnitude smaller than the flame at atmospheric pressure. The results presented further support that the use of an aluminum-lithium alloy is effective at reducing HCl produced by the propellant flame without compromising performance, thereby making it an attractive additive for solid rocket propellants.</p>

<p dir="ltr">Burning rate as a function of pressure is one of the primary evaluation metrics of solid propellants. Most solid propellant burning rate measurements are made at a nearly constant pressure using a variety of measurement approaches. This type of burning rate data is highly discretized and requires many tests to accurately determine the burning rate response to pressure. It would be moreefficient to measure burning rate dynamically as pressures are varied. Techniques used to make transient burning rate measurements are reviewed briefly and initial results using a microwave interferometry (MI) technique are presented. The MI method used in tandem with a closed bomb enables nearly continuous measurement of burning rates for self-pressurizing burns, capturing burning rate data over a wide range of pressures. This approach is especially useful for characterization of propellants with complex burning behaviors (e.g., slope breaks or mesa burning). The burning rates of three research propellants were characterized over a pressure range of 0.101-24.14 MPa (14-3500 psi). One research propellant exhibited a slope break at a pressure of 6.63 MPa (960 psi). Using MI in a closed pressure vessel, 14 propellant strand burns resulted in a nearly continuous burning rate curve over a pressure range of 0.41-24.13MPa (60-3500psi) that reasonably matched conventional burning rate measurements. The development of this technique provides an opportunity to quickly characterize the burning rate curve of solid propellants with greater fidelity and efficiency than traditional quasi-static pressure testing techniques.</p>

<p dir="ltr">Additive manufacturing (AM) of gun propellants is an emerging and promising field which addresses the limitations of conventional manufacturing techniques. Overall, this thesis is a body of work which serves to bridge the gap between fundamental research and application of additively manufactured gun propellants.</p>