Thermal aging of hydroxy-terminated polybutadiene/isophorone diisocyanate (HTPB/IPDI)-based polyurethane was studied as a function of NCO/OH ratio (1.0 and 0.85). Samples were aged in air ovens at 50, 60, 65, and 70 °C for periods of time from 1 to 34 weeks. Changes in chemical (swelling testing and FT-IR spectroscopy) and mechanical (tension testing and hardness) properties were evaluated throughout the aging assays. Correlation between equilibrium swelling ratio and elastic modulus, coupled with changes in FT-IR spectra, indicated oxidative cross-linking as the dominant mechanism for both molar ratios investigated. However, determination of Arrhenius activation energy resulted in values of (82 ± 10) kJ.mol -1 and (156 ± 30) kJ.mol -1 for 1.0 and 0.85 NCO/OH ratios, respectively, thus revealing faster oxidative degradation kinetics for higher urethane linkage networks.
The primary amine content in tetraethylenepentamine (TEPA) and TEPAN, a bonding agent used in composite solid propellants, was determined by near infrared (NIR) spectroscopy and the results were compared to those obtained by potentiometry. The band at 4930 cm−1, which showed to be influenced only by primary amine groups, was chosen as the analytical band. The calibration curves based on isopropylamine (IPA) and isopropylamine/dibutylamine (IPA/DBA) mixtures proved to be suitable for determining the NH2 content of TEPA or of samples containing mixtures of NH and NH2 groups. It was found that TEPA contains 26.4 % of NH2 and 25.7 % of NH, and that TEPAN contains 0.5 % of NH2, confirming the low content of primary amine of this bonding agent. The lowest amine equivalent of TEPA is 31.1±0.3 g/eq, as determined by potentiometry, was found because this technique measures the total hydrogen content, including primary and secondary amines. The literature value of 62.6 g/eq for TEPA ACROS obtained by potentiometry in a non aqueous medium and related to the first inflection of the primary amine, validates the value obtained by NIR in this work for a similar type of amine. The equivalent weight obtained by NIR spectroscopy (62.7 g/eq) allowed to calculate the molar mass of TEPA of 195.6 g mol−1, which is close to the typical value of 200 g mol−1.
Copper chromites are well known as burning rate catalysts for the combustion of composite solid propellants, used as a source of energy for rocket propulsion. The propellant burning rate depends upon the catalyst characteristics such as chemical composition and specific surface area. In this work, copper chromite samples from different suppliers were characterized by chemical analysis, FT-IR spectroscopy and by surface area measurement (BET). The samples were then evaluated as burning rate catalyst in a typical composite propellant formulation based on HTPB binder, ammonium perchlorate and aluminum. The obtained surface area values are very close to those informed by the catalyst suppliers. The propellant processing as well as its mechanical properties were not substantially affected by the type of catalyst. Some copper chromite catalysts caused an increase in the propellant burning rate in comparison to the iron oxide catalyst. The results show that in addition to the surface area, other parameters like chemical composition, crystalline structure and the presence of impurities might be affecting the catalyst performance. All evaluated copper chromite samples may be used as burning rate catalyst in composite solid propellant formulations, with slight advantages for the SX14, Cu-0202P and Cu-1800P samples, which led to the highest burning rate propellants.
A comparative kinetic study of the reaction of three different hydroxylated liquid polybutadienes (Mn ⋍ 3000) — R ‐ 45M, R‐45HT, and H‐034—and tolylene diisocyanate (TDI), was carried out in toluene solution. An analytical method was used to follow the kinetics of the reactions at four different temperatures. The reactions presented an apparent second‐order rate law. In the second‐order plots, a discontinuity was observed. The R‐45M polybutadiene was about twice more reactive than R‐45HT and H‐034; these latter two polybutadienes presented similar reactivities.
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