This paper reviews hydroxyl-terminal polybutadiene (HTPB) used as liner and binder for composite propellants, applied in rocket motors studied throughout the last decades, emphasizing the recent advances. The contribution aims to show the importance of HTPB in the propellant composition and on the liner coating of the rocket motor, which is in contact with the propellant grain. This paper also shows that many researchers have thoroughly studied several properties of HTPB, which are rele-vant to its role in liners and propellants. We have also reviewed analytical techniques such as Fourier Transform Infrared Spectroscopy (FTIR) as a characterization technique for HTPB and HTPB-based polyurethanes. Reflection and transfectants FTIR may be a future trend in studies about polymeric matrices for liners and propellants, and in the area of propellant formulations that use energetic binders, graphene and nanomaterials.
This review addresses a comparison, based on the literature, among nitrile rubber (NBR), ethylene-propylene-diene-monomer rubber (EPDM), and polyurethane (PU) elastomeric heat shielding materials (EHSM). Currently, these are utilized for the insulation of rocket engines to prevent catastrophic breakdown if combustion gases from propellant reaches the motor case. The objective of this review is to evaluate the performance of PU–EHSM, NBR–EHSM, and EPDM–EHSM as insulators, the latter being the current state of the art in solid rocket motor (SRM) internal insulation. From our review, PU–EHSM emerged as an alternative to EPDM–EHSM because of their easier processability and compatibility with composite propellant. With the appropriate reinforcement and concentration in the rubber, they could replace EPDM in certain applications such as rocket motors filled with composite propellant. A critical assessment and future trends are included. Rubber composites novelties as EHSM employs specialty fillers, such as carbon nanotubes, graphene, polyhedral oligosilsesquioxane (POSS), nanofibers, nanoparticles, and high-performance engineering polymers such as polyetherimide and polyphosphazenes.
Micro and nanocomposites of hydroxyl terminated polybutadiene (HTPB)-based polyurethanes (NPU) were obtained using five mineral fillers and Cloisite 20A nanoclay, respectively. Samples were prepared by the reaction of HTPB polyol and toluene diisocyanate (TDI), and the chain was further extended with glyceryl monoricinoleate to produce the final elastomeric polyurethanes. Mechanical and thermal properties were studied, showing that mineral fillers (20% w/w) significantly increased tensile strength, in particular nanoclay (at 5% w/w). When nanoclay-polymer dispersion was modified with a silane and hydantoin-bond promoter, elongation at break was significantly increased with respect to NPU with C20A. Thermal properties measured by differential scanning calorimetry (DSC) were not significantly affected in any case. The molecular structure of prepared micro and nanocomposites was confirmed by Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. Interaction of fillers with polymer chains is discussed, considering the role of silanes in compatibilization of hydrophilic mineral fillers and hydrophobic polymer. The functionalization of nanoclay with HMDS silane was confirmed using FTIR. Microstructure of NPU with C20A nanoclay was confirmed by Atomic Force Microscopy (AFM).
Polyurethane formulations utilized as liners for composite propellants were prepared by the reaction of toluene-2,4-diisocyanate (TDI) and isophorone diisocyanate (IPDI) with hydroxyl terminated polybutadiene (HTPB), while polymer chains were further extended with neopentyl glycol diol, NPG triol and two different triols (monoglyceryl ricinoleate, MRG and trimethylolpropane, TMP). Liners were formulated with micronized titanium dioxide mechanically dispersed in hydroxyl-terminated polybutadiene (HTPB). The molecular structures of liners were confirmed by FT-IR. Thermal properties indicated that the nature of chain extender (crosslinker) only slightly affected the temperatures for decomposition of liners. Two main thermal changes were found at 370∘C and another at around 440–500∘C, depending on the chain extender utilized. On the other side, mechanical properties varied within the range of 0,7-1,8 MPa, consistent with this kind of elastomers. Tensile strength at break was only significantly affected with TMP and MRG-chain extended liners at the lowest concentrations tested of 1,3 and 2% (w/w), respectively. However, the behaviour depended on whether TDI or IPDI isocyanate was utilized for curing. TMP 1,3% crosslinked liner cured with TDI had a tensile strength of 1,82MPa whileMRG-crosslinked liner cured with IPDI had a tensile strength of 1,56 MPa. It was observed that at the higher NCO/OH ratios essayed, tensile strength and hardness increased, improving mechanical properties. Our results confirmed that TMP and MRG triols together with NPG diols can be used to tailor mechanical and thermal properties of liners, considering their different hydroxyl functionalities and chain lengths.
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