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.

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.

The phase-out of chlorofluorocarbons (CFCs) has resulted in an expanding new area of research in alternative ozone friendly propellants, for example hydrofluoroalkanes (HFAs). The HFA solvent system is unique in that many CFC soluble compounds behave differently in the HFA alternatives, such as HFA-134a and HFA-227. The reason for the difference in solubility is not fully recognized. This work investigates the solubility of 22 compounds in HFA-227 with the addition of ethanol as a cosolvent. The physical properties of both solute and solvent were investigated in order to determine the effects on solubility. The solubilities of 5 compounds in HFA-134a were also investigated. A thermodynamic approach was utilized in order to look at the enthalpic and entropic effects on solubility in the propellant. Due to the high vapor pressure of propellants, a liquid model was utilized, owing to its ease of use in characterizing solubility. The correlation between the liquid model 2H,3H-decafluoropentane (DFP) and the propellants HFA-134a and HFA-227 was examined.The solubilities in HFA-227 with ethanol ranged from 0.001 to 3.282 %w/w, where the solubilities always increase when ethanol was added. The experimental solubilities were compared to calculated values obtained from ideal solubility and regular solution theory models. A clear correlation with the ideal solubility (melting point) combined with an intercept term and two physical properties was noted. A regression approach was also used to predict the activity coefficient in HFA-227 with 0 - 20% ethanol. These equations were combined with the extended ideal solubility equation, creating a useful predictive equation with AAE values ranging from 0.32 to 0.36, or factor errors of 2.09 to 2.29. The equations shown in this work are useful for the prediction of solute solubility in HFA-227/ethanol mixtures.Results in the liquid model DFP with 0 - 20% ethanol show that a regression equation results in a useful predictive equation for the solubilities in both HFA-134/ethanol and HFA-227/ethanol systems, where the AAE values ranged from 0.3 to 0.56, or factor errors of 2.0 to 3.6.The solubilities of a series of chlorobenzene compounds along with a group of hydrogen donating and/or accepting compounds was examined in HFA-134a. The entropic effects appear to be the limiting factor in the solubility of these compounds. The compounds capable of hydrogen accepting and donating exhibited negative enthalpy of mixing values when placed in HFA-134a, a stark contrast to the values obtained for the chlorobenzenes. This suggests HFA-134a is able to strongly interact with solutes capable of donating or accepting hydrogen.

No description available.

Approved for public release; distribution is unlimited / An investigation into the behavior of aluminized solid propellant combustion in a two-dimensional windowed rocket motor was conducted using holographic techniques. Holograms were recorded in the motor port, aft of the propellant grain and at the entrance to the exhaust nozzle for two different propellant compositions at varying operating pressures. Quantitative particle size data for particles larger than 20 microns were obtained from the holograms. From these data, the mean diameters (D32) of the larger particles were calculated and utilized to compare what effects pressure, location in the motor and aluminum content had on the behavior of the aluminum/aluminum oxide particles. D 32 was found to decrease with increasing pressure, but was unaffected by variations in low values of propellant aluminum loading. D 32 at the grain exit was found to be significantly less than within the grain port. / http://archive.org/details/holographicinves00butl / Lieutenant, United States Navy

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 self-sustained 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.

No description available.

Thesis (M.S.)--Ohio State University, 1986. / Includes bibliographical references (leaf 77).

The present studies are concerned with the modelling of the manufacturing process of nitrocellulose-base propellant in which cellulose acetate is substituted as a model for the explosive nitrocellulose. An investigation of the inter-relationships between processing and rheological and morphological properties has been carried out on cellulose acetate doughs, using modified torque and capillary extrusion rheometers. Some of the doughs show a yield stress and behave as Herschel-Bulkley fluids. The yield stress is found to be smaller than that of nitrocellulose doughs, and there is some evidence of shear heating. Mixing time and mixing temperature showed no influence on the rheological parameters of the doughs. These results suggest that the change in rheological properties of propellant doughs is attributed to the change in crystallinity and fibrosity after processing. The rheological properties of doughs are greatly affected by extrusion temperature, solvent, plasticiser and filler content. The interaction between the solvents and plasticisers with cellulose acetate was explained by adopting a model consisting of a rigid backbone chain from which protruded flexible side groups. In good solvents these side groups extend causing interactions between molecules, giving rise to dough up and elasticity. In poor solvents, dough up becomes difficult and the elasticity is low because the flexible side groups retract towards the stiff backbone chain. The morphology of solvated doughs is examined using solution viscometry, infrared spectroscopy, scanning electron microscope, differential scanning calorimetry, x-ray diffraction and dynamic mechanical thermal analysis. All these techniques showed that the solvation process had no significant effect on the molecular architecture of the cellulose acetate, in which the original crystallinity of the material is low. From this it was concluded that changes in the rheological properties of nitrocellulose doughs as a function of the process variables was due to changes induced in the crystallites rather than in the amorphous regions.

A method for developing an erosive burning model for use in solid propellant design-and-analysis interior ballistics codes is described and evaluated. Using Direct Numerical Simulation, the primary mechanisms controlling erosive burning (turbulent heat transfer, and finite rate reactions) have been studied independently through the development of models using finite rate chemistry, and infinite rate chemistry. Both approaches are calibrated to strand burn rate data by modeling the propellant burning in an environment with no cross-flow, and adjusting thermophysical properties until the predicted regression rate matches test data. Subsequent runs are conducted where the cross-flow is increased from M=0.0 up to M=0.8. The resulting relationship of burn rate increase versus Mach Number is used in an interior ballistics analysis to compute the chamber pressure of an existing solid rocket motor. The resulting predictions are compared to static test data. Both the infinite rate model and the finite rate model show good agreement when compared to test data. The propellant considered is an AP/HTPB with an average AP particle size of 37 microns. The finite rate model shows that as the cross-flow increases, near wall vorticity increases due to the lifting of the boundary caused by the side injection of gases from the burning propellant surface. The point of maximum vorticity corresponds to the outer edge of the APd-binder flame. As the cross-flow increases, the APd-binder flame thickness becomes thinner; however, the point of highest reaction rate moves only slightly closer to the propellant surface. As such, the net increase of heat transfer to the propellant surface due to finite rate chemistry affects is small. This leads to the conclusion that augmentation of thermal transport properties and the resulting heat transfer increase due to turbulence dominates over combustion chemistry in the erosive burning problem. This conclusion is advantageous in the development of future models that can be calibrated to heat transfer conditions without the necessity for finite rate chemistry. These results are considered applicable for propellants with small, evenly distributed AP particles where the assumption of premixed APd-binder gases is reasonable.