The relationship between the physicochemical properties of asphaltenes and asphaltene structure is an issue of increasing focus. Surface pressure-area isotherms of asphaltene model compounds have been investigated to gain more knowledge of their arrangement at an aqueous surface. Variations in interfacial activity have been correlated to proposed arrangements. The presence of a carboxylic acid has shown to be crucial for their interfacial activity and film properties. The acid group directs the molecules normal to the surface, forming a stable monolayer film. The high stability was absent when no acidic groups were present. Fluorescence spectra of deposited Langmuir-Blodgett films showed only the presence of the excimer emission for thin films of acidic model compounds, indicating a close face-to-face arrangement of the molecules. Time-correlated single photon counting (TCSPC) of the model compounds in toluene indicated the presence of aggregates for two of four compounds at low concentrations. However, a sudden drop of interfacial tension observed could not be correlated to the aggregation. Instead, aggregation induced by addition of a "poor" solvent showed decreased interfacial activity when aggregated due to decrease of monomers in bulk. The findings regarding these asphaltene model compounds and their structural differences show the great effect an acidic group has on their physicochemical properties.
Very few efficient bonding agents for use in solid rocket propellants with nitramine filler materials and energetic binder systems are currently available. In this work, we report the synthesis, detailed characterization, and use of neutral polymeric bonding agents (NPBA) in isocyanate‐cured and smokeless composite rocket propellants based on the nitramine octogen (HMX), the energetic binder glycidyl azide polymer (GAP), and the energetic plasticizer N‐butyl‐2‐nitratoethylnitramine (BuNENA). These polymeric bonding agents clearly influenced the viscosity of the uncured propellant mixtures and provided significantly enhanced mechanical properties to the cured propellants, even at low NPBA concentrations (down to 0.001 wt‐% of propellant). A modified NPBA more or less free of hydroxyl functionalities for interactions with isocyanate curing agent provided the same level of mechanical improvement as regular NPBA containing a substantial number of reactive hydroxyl groups. However, some degree of reactivity towards isocyanate is essential for function.
Traditional composite rocket propellants are cured by treatment of hydroxyl‐terminated prepolymers with polyfunctional aliphatic isocyanates. For development of smokeless composite propellants containing nitramines and/or ammonium dinitramide (ADN), energetic binder systems using glycidyl azide polymer (GAP) are of particular interest. Polyfunctional alkynes are potential isocyanate‐free curing agents for GAP through thermal azide‐alkyne cycloaddition and subsequent formation of triazole crosslinkages. Propargyl succinate or closely related aliphatic derivatives have previously been reported for such isocyanate‐free curing of GAP. Herein, we present the synthesis and use of a new aromatic alkyne curing agent, the crystalline solid bisphenol A bis(propargyl ether) (BABE), as isocyanate‐free curing agent in smokeless propellants based on GAP, using either octogen (HMX) and/or prilled ADN as energetic filler materials. Thermal and mechanical properties, impact and friction sensitivity and ballistic characteristics were evaluated for these alkyne cured propellants. Improved mechanical properties could be obtained by combining isocyanate and alkyne curing agents (dual curing), a combination that imparted better mechanical properties in the cured propellants than either curing system did individually. The addition of a neutral polymeric bonding agent (NPBA) for improvement of binder‐filler interactions was also investigated using tensile testing and dynamic mechanical analysis (DMA). It was verified that the presence of isocyanates is essential for the NPBA to improve the mechanical properties of the propellants, further strengthening the attractiveness of dual cure systems.
Ammonium dinitramide (ADN) is a high performance solid oxidizer of interest for use in high impulse and smokeless composite rocket propellant formulations. While rocket propellants based on ADN may be both efficient, clean burning, and environmentally benign, ADN suffers from several notable disadvantages such as pronounced hygroscopicity, significant impact and friction sensitivity, moderate thermal instability, and numerous compatibility issues. Prilled ADN is now a commercially available and convenient product that addresses some of these disadvantages by lowering the specific surface area and thereby improving handling, processing, and stability. In this work, we report the preparation, friction and impact sensitivity and mechanical properties of several smokeless propellant formulations based on prilled ADN and isocyanate cured and plasticized glycidyl azide polymer (GAP) or polycaprolactone‐polyether. We found such propellants to have very poor mechanical properties in unmodified form and to display somewhat unreliable curing. However, by incorporation of octogen (HMX) and a neutral polymeric bonding agent (NPBA), the mechanical properties of such smokeless formulations were significantly improved. Impact and friction sensitivities of these propellants compare satisfactorily with conventional propellants based on ammonium perchlorate (AP) and inert binder systems.
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