Transition Metal Complexes of Dibenzyl Tetraazamacrocycles

Tetraazamacrocycles, cyclic molecules with four nitrogen atoms, have long been known to produce highly stable transition metal complexes. Cross-bridging such molecules with 2-carbon chains has been shown to enhance the stability of these complexes even further, providing enough stability to use the resulting compounds in applications as diverse and demanding as aqueous, green oxidation catalysis all the way to drug molecules injected into humans. Although the stability of these compounds is believed to result from the increased rigidity and topological complexity imparted by the cross-bridge, there is insufficient experimental data to exclude other causes. In this study, standard organic and inorganic synthetic methods were used to produce unbridged dibenzyl tetraazamacrocycle analogues of known cross-bridged tetraazamacrocycles and their transition metal complexes to allow direct comparison of molecules identical except for the cross-bridge. The syntheses of the known tetraazamacrocycles and the novel transition metal complexes were successful with high yields and purity. Initial chemical characterization of the complexes by UV-Visible spectroscopy and cyclic voltammetry shows little difference in electronic properties from bridged versions. Direct comparison studies of the unbridged and bridged compounds’ stabilities remain to be carried out and will shed light on the importance of the cross-bridge to complex robustness

CHARACTERIZATION OF DAMAGED MATERIALS

Thermal damage experiments were conducted on LX-04, LX-10, and LX-17 at high temperatures. Both pristine and damaged samples were characterized for their material properties. A pycnometer was used to determine sample true density and porosity. Gas permeability was measured in a newly procured system (diffusion permeameter). Burn rate was measured in the LLNL strand burner. Weight losses upon thermal exposure were insignificant. Damaged pressed parts expanded, resulting in a reduction of bulk density by up to 10%. Both gas permeabilities and burn rates of the damaged samples increased by several orders of magnitude due to higher porosity and lower density. Moduli of the damaged materials decreased significantly, an indication that the materials became weaker mechanically. Damaged materials were more sensitive to shock initiation at high temperatures. No significant sensitization was observed when the damaged samples were tested at room temperature

SHOCK INITIATION EXPERIMENTS ON THE HMX BASED EXPLOSIVE LX-10 WITH ASSOCIATED IGNITION AND GROWTH MODELING

Shock initiation experiments on the HMX based explosives LX-10 (95% HMX, 5% Viton by weight) and LX-07 (90% HMX, 10% Viton by weight) were performed to obtain in-situ pressure gauge data, run-distance-to-detonation thresholds, and Ignition and Growth modeling parameters. A 101 mm diameter propellant driven gas gun was utilized to initiate the explosive samples with manganin piezoresistive pressure gauge packages placed between sample slices. The run-distance-to-detonation points on the Pop-plot for these experiments and prior experiments on another HMX based explosive LX LX-04 (85% HMX, 15% Viton by weight) will be shown, discussed, and compared as a function of the binder content. This parameter set will provide additional information to ensure accurate code predictions for safety scenarios involving HMX explosives with different percent binder content additions

Threat and error management for anesthesiologists: a predictive risk taxonomy

Patient care in the operating room is a dynamic interaction that requires cooperation among team members and reliance upon sophisticated technology. Most human factors research in medicine has been focused on analyzing errors and implementing system-wide changes to prevent them from recurring. We describe a set of techniques that has been used successfully by the aviation industry to analyze errors and adverse events and explain how these techniques can be applied to patient care

Energy Index For Aircraft Maneuvers

Method and system for analyzing, separately or in combination, kinetic energy and potential energy and/or their time derivatives, measured or estimated or computed, for an aircraft in approach phase or in takeoff phase, to determine if the aircraft is or will be put in an anomalous configuration in order to join a stable approach path or takeoff path. A 3 reference value of kinetic energy andor potential energy (or time derivatives thereof) is provided, and a comparison index .for the estimated energy and reference energy is computed and compared with a normal range of index values for a corresponding aircraft maneuver. If the computed energy index lies outside the normal index range, this phase of the aircraft is identified as anomalous, non-normal or potentially unstable

MEASUREMENT OF MATERIAL PROPERTIES OF DAMAGED ENERGETIC MATERIALS

We recently conducted damaged experiments on three explosives (mechanical damage on LX-04 and thermal experiments on HPP and PBXN-9) and characterized the effect of damage on some material properties. The MTS equipment was used to apply compressive cycling to LX-04 pressed parts and the results showed that older LX-04 parts became mechanically weaker than newer parts. After repeated compressive cycling for over 20,000 times, older LX-04 parts failed but newer LX-04 parts survived. Thermal insults were applied to PBXN-9 and HPP at 180 C and 200 C, respectively in unconfined conditions for several hours. The thermally-damaged HPP sample suffered 12.0% weight losses and a volume expansion of 20% was observed. Porosity of the damaged HPP increased to 25% after thermal exposure, which led to higher gas permeability. Burn rates of damaged PBXN-9 were 2 orders of magnitude higher than those of pristine samples but burn rates of damaged HPP were only slightly higher than those of pristine HPP. Small-scale safety tests (impact, friction, and spark) showed no significant sensitization when the damaged samples were tested at room temperature. Gas permeation measurements showed that gas permeability in damaged materials was several orders of magnitude higher than that in pristine materials. In-situ measurements of gas permeability at high temperatures were made on HPP samples and the results showed that the gas permeability increased by 3 to 4 orders of magnitude

LOW AMPLITUDE SINGLE AND MULTIPLE SHOCK INITIATION EXPERIMENTS AND MODELING OF LX-04

Shock initiation experiments were performed on the plastic bonded explosive (PBX) LX-04 (85% HMX, 15% Viton binder) using single and multiple low amplitude shocks to obtain pressure history data for use in Ignition and Growth reactive flow modeling parameterization. A 100 mm diameter propellant driven gas gun was utilized to initiate the LX-04 explosive charges containing manganin piezoresistive pressure gauge packages placed between explosive discs. In the single shock experiments, the run distances to detonation at three shock pressures showed agreement with previously published data above 3 GPa. Even longer run distances to detonation were measured using 80 mm long by 145 mm diameter LX-04 charges impacted by low velocity projectiles from a 155 mm diameter gun. The minimum shock pressure required to cause low levels of exothermic reaction were determined for these large LX-04 charge dimensions. Multiple shocks were generated as double shocks by using a flyer plate with two materials and as reflected shocks by placing a high impedance material at the rear of the explosive charge. In both cases, the first shock pressure was not high enough to cause detonation of LX-04, and the second shock pressure, which would have been sufficient to cause detonation if generated by a single shock, failed to cause detonation. Thus LX-04 exhibited shock desensitization over a range of 0.6 to 1.4 GPa. The higher shock pressure LX-04 model was extended to accurately simulate these lower pressure and multiple shock gauge records. The shock desensitization effects observed with multiple shock compressions were partially accounted for in the model by using a critical compression corresponding to a shock pressure of 1.2 GPa. This shock desensitization effect occurs at higher pressures than those of other HMX-based PBX's containing higher HMX percentages

SHOCK INITIATION EXPERIMENTS ON PBX 9501 EXPLOSIVE AT PRESSURES BELOW 3 GPa WITH ASSOCIATED IGNITION AND GROWTH MODELING

Shock initiation experiments on the explosive PBX 9501 (95% HMX, 2.5% estane, and 2.5% nitroplasticizer by weight) were performed at pressures below 3 GPa to obtain in-situ pressure gauge data, run-distance-to-detonation thresholds, and Ignition and Growth modeling parameters. Propellant driven gas guns (101 mm and 155 mm) were utilized to initiate the PBX 9501 explosive with manganin piezoresistive pressure gauge packages placed between sample slices. The run-distance-to-detonation points on the Pop-plot for these experiments showed agreement with previously published data and Ignition and Growth modeling parameters were obtained with a good fit to the experimental data. This parameter set will allow accurate code predictions to be calculated for safety scenarios in the low-pressure regime (below 3 GPa) involving PBX 9501 explosive