| المؤلفون: |
Powell MS; Maurice J. Zucrow Laboratory, Mechanical Engineering Department, Purdue University, 500 Allison Rd., West Lafayette, Indiana 47907, United States.; Shock and Detonation Physics, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Sakano MN; Neil Armstrong Hall of Engineering, School of Materials Engineering, Purdue University, 701 West Stadium Avenue, West Lafayette, Indiana 47907, United States., Cawkwell MJ; Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Bowlan PR; Physical Chemistry and Applied Spectroscopy, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Brown KE; Shock and Detonation Physics, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Bolme CA; Shock and Detonation Physics, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Moore DS; Shock and Detonation Physics, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States., Son SF; Maurice J. Zucrow Laboratory, Mechanical Engineering Department, Purdue University, 500 Allison Rd., West Lafayette, Indiana 47907, United States., Strachan A; Neil Armstrong Hall of Engineering, School of Materials Engineering, Purdue University, 701 West Stadium Avenue, West Lafayette, Indiana 47907, United States., McGrane SD; Shock and Detonation Physics, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States. |
| مستخلص: |
Thin films of pentaerythritol tetranitrate (PETN) were shock compressed using the laser driven shock apparatus at Los Alamos National Laboratory (LANL). Two spectroscopic probes were available to this apparatus: visible white light transient absorption spectroscopy (VIS) from 400 to 700 nm and mid-infrared transient absorption spectroscopy (MIR) from 1150 to 3800 cm -1 . Important PETN vibrational modes are the symmetric and antisymmetric NO 2 stretches at 1280 and 1650 cm -1 , respectively, as well as CH stretches at ∼2900 cm -1 . Shock strength was varied from approximately 3 to 55 GPa to span from the chemically unreactive regime to the regime in which fast chemical reaction took place on the 250 ps time scale of the measurements. VIS and MIR results suggest irreversible chemistry was induced in PETN at pressures above 30 GPa. At lower shock pressures, the spectroscopy showed minimal changes attributable to pressure induced effects. Under the higher-pressure reactive conditions, the frequency region at the antisymmetric NO 2 stretch mode had a significantly increased absorption while the region around the symmetric NO 2 stretch did not. No observable increased absorption occurred in the higher frequency regions where CH-, NH-, and OH- bond absorptions would be observed. A broad absorption appeared on the shoulder at the red-edge of the CO 2 vibrational band around 2200 cm -1 . In addition to the experiments, reactive molecular dynamics were carried out under equivalent shock conditions to correlate the evolution of the infrared spectrum to molecular processes. The simulations show results consistent to experiments up to 30 GPa but suggest that NO and NO 2 related features provided the strongest contributions to the shocked infrared changes. Proposed mechanisms for shocked PETN chemistry are analyzed as consistent or inconsistent with the data presented here. Our experimental data suggests C≡O or N 2 O bond formation, nitrite formation, and absence of significant hydroxyl or amine concentrations in the initial chemistry steps in PETN shocked above 30 GPa. |
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