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Optimization of Curing Agents for Linear Difunctional Glycidyl Azide Polymer (GAP), with and without Isocyanate, for Binder Applications

Agawane N. T., Soman R. R., Wagh R. M., Athar J., Talawar M.

Central European Journal of Energetic Materials

2018

Vol. 15, no. 1

206--222

Glycidyl Azide Polymer (GAP) is one of the most potential energetic binders for rocket propellants and gas generator compositions. In the present paper GAP of molecular weight (Mn) ~2000 was cured with a mixture of di- and tri-isocyanates without a cross linker. The curing profile and time of curing was recorded using a rheometer. The minimum curing time was observed for samples cured with Desmodour N-100 alone, whereas the maximum curing time was observed for samples cured with a mixture of Desmodour N-100 and Isophorone Diisocyanate (IPDI) (1:1 w/w). It was observed that all of the samples cured well and were void or bubble free. The mechanical properties data showed that the tensile strength (TS) of GAP cured with Desmodour N-100 alone was 1.19 kgf/cm2, which is a minimum, while the maximum TS (3.66 kgf/cm2) was achieved with a mixture of N-100 and 4,4’methylenebis(phenylisocynate) (MDI). The percent elongation for a sample cured with Desmodour N-100 was 160, and was reduced to 64.27 when a mixture of MDI and N-100 was used. In order to study the curing of GAP without an isocyanate, GAP diol was cured with hexanediol di-acrylate. GAP was also cured with an alkyne-based curing agent i.e. bis-propargyl succinate (BPS), which showed improved curing. Comparative thermal studies of GAP cured with isocyanate and acrylate was carried out. Differential Scanning Calorimetry (DSC) and Simultaneous Thermal Analysis (STA) curves for all of the cured samples were recorded in order to study and compare the thermal decomposition behaviour of the cured GAP. Isocyanate cured GAP exhibited a single stage decomposition, with larger heat output. Acrylate cured GAP exhibited a two stage decomposition. Finally, a mixture of IPDI and Desmodour N-100 was selected for curing of GAP. Accordingly, curing was carried out and was tested in a small ballistic evaluation motor (BEM) to observe the combustion behaviour and burn rate. From the pressure-time profile it was found that this composition gave smooth burning with a pressure of ~3 kg/sec2 for 7 seconds of burn.

Research on the Mechanical Properties and Curing Networks of Energetic GAP/TDI Binders

Ma S., Li Y., Li Y., Li G., Luo Y.

Central European Journal of Energetic Materials

2017

Vol. 14, no. 3

708--725

This research focused on correlations between the macroscopic mechanical performance and microstructures of energetic binders. Initially a series of glycidyl azide polymer (GAP)/toluene diisocyanate (TDI) binders, catalyzed by a mixture of dibutyltin dilaurate (DBTDL) and triphenyl bismuth (TPB), was prepared. Uniaxial tensile testing, and low-field nuclear magnetic resonance and infrared spectroscopy were then used to investigate the mechanical properties, curing networks, and hydrogen bonding (H-bonds) of these binders. Additionally, a novel method based on the molecular theory of elasticity and the statistical theory of rubber elasticity was used to analyze the integrity of the networks. The results showed that the curing parameter R strongly influences the mechanical properties and toughness of the binders, and that a tensile stress (σm) of 1.6 MPa and an elongation (εm) of 1041% was observed with an R value of 1.6. The cross-linking density increased sharply with the curing parameter, but only modestly with an R value ≥ 1.8. The proportion of H-bonds formed by the imino groups increased with the R value and reached 72.61% at an R value of 1.6, indicating a positive correlation between the H-bonds and σm. Molecular entanglement was demonstrated to increase with R and to contribute dramatically to the mechanical performance. The integrity of these networks, evaluated by a correction factor (A), varies with R, and a network of the GAP/TDI binder with an R value of 1.6 is desirable.