Combustion characteristics of SMX and SMX based propellants

David A Reese, Purdue University

Abstract

This work investigates the combustion of the new solid nitrate ester 2,3-hydroxymethyl-2,3-dinitro-1,4-butanediol tetranitrate (SMX, C6H 8N6O16). SMX was synthesized for the first time in 2008. It has a melting point of 85 °C and oxygen balance of 0% to CO 2, allowing it to be used as an energetic additive or oxidizer in solid propellants. In addition to its neat combustion characteristics, this work also explores the use of SMX as a potential replacement for nitroglycerin (NG) in double base gun propellants and as a replacement for ammonium perchlorate in composite rocket propellants. The physical properties, sensitivity characteristics, and combustion behaviors of neat SMX were investigated. Its combustion is stable at pressures of up to at least 27.5 MPa (n = 0.81). The observed flame structure is nearly identical to that of other double base propellant ingredients, with a primary flame attached at the surface, a thick isothermal dark zone, and a luminous secondary flame wherein final recombination reactions occur. As a result, the burning rate and primary flame structure can be modeled using existing one-dimensional steady state techniques. A zero gas-phase activation energy approximation results in a good fit between modeled and observed behavior. Additionally, SMX was considered as a replacement for nitroglycerin in a double base propellant. Thermochemical calculations indicate improved performance when compared with the common double base propellant JA2 at SMX loadings above 40 wt-%. Also, since SMX is a room temperature solid, migration may be avoided. Like other nitrate esters, SMX is susceptible to decomposition over long-term storage due to the presence of excess acid in the crystals; the addition of stabilizers (e.g., derivatives of urea) during synthesis should be sufficient to prevent this. the addition of Both unplasticized and plasticized propellants were formulated. Thermal analysis of unplasticized propellant showed a distinct melt-recrystallization curve, which indicates that a solid phase solution is being formed between SMX and NC, and that SMX would not act as plasticizer. Analysis of propellant prepared with diethyleneglycol dinitrate (DEGDN) plasticizer indicates that the SMX is likely dissolved in the DEGDN. The plasticized material also showed similar hardness and modulus to JA2. However, both plasticized and unplasticized propellants exhibited deconsolidated burning at elevated pressures due to the high modulus of the propellant. Increased amounts of plasticizer or improved processing of the nitrocellulose should be investigated to remedy this issue. Safety characterization showed that sensitivity of the plasticized propellant is similar to JA2. In short, replacing NG with SMX results in a new family of propellants with acceptable safety characteristics and which may also offer improved theoretical performance. Finally, composite propellants based on SMX were theoretically and experimentally examined and compared to formulations based on ammonium perchlorate (AP). Thermochemical equilibrium calculations show that aluminized SMX-based formulations can achieve theoretical sea level specific impulse values upwards of 260 s– slightly lower than an AP-based composite. Both ignition sensitivity (tested via drop weight impact, electro-static discharge, and BAM friction) and physical properties (hardness and thermal properties) are comparable to those of the AP-based formulations. However, the SMX-based formulation could be detonated using a high explosive donor charge in contact with the propellant, as do other low smoke propellants. Differential scanning calorimetry of the SMX-based propellant indicated an exotherm onset of 140 °C, which corresponds to the known decomposition temperature of SMX. The propellant has a high burning rate of 1.57 cm/s at 6.89 MPa, with a pressure exponent of 0.85. This high pressure sensitivity might be addressed using various energetic and/or stabilizing additives. With high density and performance, smokeless combustion products, and stable combustion, SMX appears to be a viable replacement for existing energetic ingredients in a wide variety of propellant, explosive, and pyrotechnic applications.

Degree

Ph.D.

Advisors

Groven, Purdue University.

Subject Area

Physical chemistry|Aerospace engineering|Mechanical engineering|Astronomy

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