Composite solid propellants have used cast molding production technology for many decades, with intrinsic limitations on production flexibility, promptness, and grain geometry, as well as environmental implications on toxicity and global carbon footprint. This traditional method involves the use of toxic chemicals, has a long processing time, requires high temperature, and the products have limited geometries. To overcome those issues, different photo-curable resins have been evaluated as possible matrices. In fact, the UV-curing process is fast and has low energy consumption. The photocuring reaction parameters of six different pristine formulations were evaluated by Fourier transform infrared spectroscopy analysis. After finding the optimal curing parameters, different composites were prepared by adding 75 or 80 wt% ammonium sulfate particles used as an inert replacement for the oxidant. The thermomechanical properties and thermal resistance of the UV-cured composites were characterized via dynamic thermal-mechanical and thermogravimetric analysis. Subsequently, the mechanical properties of the inert propellants were investigated by tensile tests. The most promising resin systems for the production of solid rocket propellants were then 3D printed by an in-house developed illumination system and the obtained object micro-structure was evaluated by X-ray computed tomography.

This study delves into the rheological and mechanical properties of a 3D-printable composite solid propellant with 80% wt solids loading. Polybutadiene is used as a binder with ammonium sulfate, which is added as an inert replacement for the ammonium perchlorate oxidizer. Further additives are introduced to allow for UV curing. An in-house illumination system made of four UV-A LEDs (385 nm) is employed to cure the resulting slurry. Rheological and mechanical tests are conducted to evaluate the viscosity, ultimate tensile strength and strain, and compression behavior. Viscosity tests are performed for both pure resin and complete propellant composition. A viscosity reduction factor is obtained for the tested formulations when pre-heating slurry. Uniaxial tensile and compression tests reveal that the mechanical properties are consistent with previous research. Results emphasize the critical role of temperature and solid loading percentage. Pre-heating resin composites may grant a proper viscosity reduction while keeping mechanical properties in the applicability range. Overall, these findings pave the way for the development of a 3D printer prototype for composite solid propellants.

Challenges in the traditional cast-and-cure manufacturing of composite solid propellants, such as the use of mandrels and the toxicity of curing agents, are being addressed through new propellant formulations and additive manufacturing techniques. Within this framework, this study aimed to investigate the properties of UV-curable composite solid rocket propellants, focusing on their compatibility with advanced 3D printing technologies. Polybutadiene-based propellants incorporating a specific photoinitiator were examined. Key rheological properties, including the pseudoplasticity and pot-life, were assessed to evaluate the material’s behavior during the printing process. Furthermore, photopolymerization tests were performed using a customized delta illuminator to evaluate the conversion efficiency under UVA and UVC light sources. Concurrently, a modular Cartesian 3D printer was developed and preliminary tests were performed. Rheological tests also revealed a flow index n of 0.32 at 60 °C and 0.46 at 80 °C, indicating significant pseudoplastic behavior. The pot-life tests showed that the viscosity of the propellant reached the upper limit of ${10}^6$ cP more quickly at higher temperatures, indicating a shorter time range of printability. UVA irradiation resulted in a polymerization conversion rate of about 90%, while UVC exposure did not significantly enhance the conversion rate beyond this value. Finally, the 3D printing tests confirmed the feasibility of producing solid propellant, though challenges related to material segregation and the extrusion consistency were observed. Material separation resulted in a significant impact on the printability, causing underextrusion and nozzle clogging, particularly with smaller nozzle diameters and higher extrusion pressures. Overall, this research represents a significant step forward in the development of UV-curable propellants for additive manufacturing, building on previous advancements by the research group. It demonstrates tangible progress in addressing key challenges such as the printability, material performance, and curing efficiency, while also highlighting areas requiring further refinement. These findings underscore the continuous evolution of this technology toward higher readiness levels, paving the way for its broader application in composite solid propellant manufacturing.

This work explores solid rocket motor grain design, leveraging additive manufacturing techniques based on slurry deposition and UV-curing. The objective is to develop an automated design procedure to identify optimal solutions that meet mission requirements, exploiting new geometries and ballistic configurations previously unattainable with the classical mix–cast–cure manufacturing process. The design procedure is based on a stochastic optimization approach coupled with surrogate modeling of the pressure–time response, considering variable geometrical and ballistic parameters. Several surrogate models were tested after the creation of suitable databases through the computation of pressure evolution for different configurations. The most appropriate surrogate model was selected and applied within optimization routines to evaluate individual designs. The optimizer identifies the most suitable configuration to obtain the desired pressure–time response and to meet motor requirements. Different design approaches have been tested to evaluate the ballistic distribution’s influence on performance and how it can be leveraged to meet requirements, even with significant modifications in grain geometry. The results show that the proposed procedure is able to effectively achieve the expressed requirements, successfully handling the novel design environment. Furthermore, they highlight the strong influence of the ballistic distribution on performance and show how it can be successfully exploited to guide grain design.