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The work presented here aimed at developing advanced thermoplastic composite laminates specifically dedicated to the fabrication of brush-armature supporting structures for the PEGASUS railgun of the French-German Research Institute of Saint-Louis. The main objective is to surpass the results obtained previously with glass-fiber-reinforced epoxy composites. Due to higher ductility and superior dynamic behavior of PEEK polymers, an S2-glass woven fabric preimpregnated with a PEEK resin was selected. The interlaminar resistance and tensile behavior of the material was characterized experimentally. The results led to the identification of the most suitable fiber/resin ratio and fabrication process for thick laminates. Several prototypes weighing about 320 g were produced and used for six shots with the PEGASUS railgun. Already in the first series of experiments, the laminates show a remarkable mechanical resistance, and a maximal velocity of 2440 m/s was obtained.