Publications

Energetic materials, such as high explosives, propellants and ballotechnics, are widely used as energy sources in the design of numerous devices, components and processes. Although most energetic materials are selected for safe operation, their high energy densities have the potential for inadvertent initiation and subsequent powerful energy transformations. This potential for damage or injury places a heavy burden on careful analysis of safety issues as part of the design process. As a result, considerable effort has been devoted to empirical testing of initiation conditions, and development of scientific models of initiation processes that have been incorporated into computer models for numerical simulation of initiation of reaction. Nevertheless, in many cases, there is still only rudimentary understanding of the processes of initiation. Mechanochemical processes are perhaps the least understood of the various excitation mechanisms. In these energy transformation processes mechanical stimuli lead directly to initiation and substantial reaction under conditions not thought to be capable of reaction. There are no established scientific models of the initiation of mechanochemical reactions in energetic materials. Mechanochemical reactions can be initiated by enhanced solid state chemical reactivity, changes in reactant configuration, and localization of initiation energy. Such solid state reactions are difficult to understand, either empirically or scientifically, as they are inherently nonequilibrium processes; scientific models currently used assume equilibrium thermochemical conditions and materials behaviors. The present work was undertaken as a first step in developing a scientific basis for prediction of the initiation of mechanochemical processes in high energy density solids.

The authors report about the shock-compression response of highly porous (55% and 65% dense) mixtures of 4Al + 3SiO{sub 2} powders having shock-induced phase transitions and chemical reactions. Shock recovery experiments were performed using the CETR/Sawaoka plate-impact system (P = 40 to 100 GPa) and the Sandia Momma Bear A Comp B fixture (P = 22 to 45 GPa). The recovered compacts contained the high pressure stishovite phase, products of chemical reaction, as well as unreacted constituents. The reaction products formed included Al{sub 2}O{sub 3} metallic Si (ambient and high pressure phases), SiAl intermetallic, and kyanite (Al{sub 2}SiO{sub 5}). The shock-induced chemical reaction in 4Al + 3SiO{sub 2} powder mixtures, appears to have been accompanied (or assisted) by the formation of stishovite, a high pressure phase of quartz.

Simulations with finite element models of well controlled impact experiments with x-cut quartz gauges have been performed with the transient electromechanics code SUBWAY. Comparisons of measured gauge output current with calculated output current were made for four fully-electroded gauge configurations, involving two different can spacings and potting materials. The observed good agreement between measured and calculated currents provides a basis for confidence in the basic capabilities of the code.

Prior work has shown that the piezoelectric response of shock-compressed PVDF film prepared with attention to mechanical and electrical processing exhibits precise, well-defined, reproducible behavior to 10 GPa. Higher pressure response continues to pressures approaching 50 GPa, and appears to provide a basis for a very high pressure stress-rate gauge. Previous work shows that differences in response were sometimes observed. The present report describes studies in progress undertaken to increase the precision of the polarization of the PVDF and to develop optimum sensors and shock gauge package designs. Results obtained on such careful prepared PVDF shock gauges show that differences in electrical charge response less than few percent are observed between 10 and 25 GPa.

Short communication.

Highly reactive coal pyrites and unstable museum specimens are easily distinguished from the stable pyrites by the growth of white crystals that cover samples exposed to room atmosphere for short periods of time. Continued exposure to the atmosphere will eventually cause the specimens to fall apart. The term rotten pyrite has been applied to museum specimens that fall apart in this way. SEM studies show that reactive (rotten) pyrites contain between 100 and 10,000 times more dislocations than stable pyrites. Shock-loading of a stable pyrite to 7.5 GPa and 17 GPa increased its reactivity by a factor of two, probably caused by an increase in the number of imperfections. However, shock-loading at 22 GPa decreased the reactivity of pyrite because the imperfections produced at the higher pressure were removed during annealing the sample received at the higher temperature. Although there was a factor of six difference between the most and least reactive shocked MCB (commercial pyrite) samples, shock-loading did not increase the reactivity of the MCB pyrite to that of the Queensland coal pyrite. The results in hand show that while shock-loading produces sufficient imperfections to increase the reactivity of pyrites, there is insufficient data to show that imperfections are the main reason why some coal pyrites are highly reactive. 9 refs., 1 fig., 1 tab.

Shock-induced reaction synthesis (SRS) is used for solid state processing of Ni-Al, Ni-Si, and Nb-Si type compounds, starting with elemental powder mixtures. The constituent elemental powders are blended in different stoichiometries and packed at 65% density in stainless steel capsules. A steel flyer plate, accelerated by the detonation of an explosive, impacts the powder containing capsules embedded in a steel recovery fixture backed by a momentum trap. The shock wave generated upon impact triggers a self-sustaining, exothermic reaction between the elemental powder constituents, thereby synthesizing the compound and at the same time consolidating the porous mass into 12mm diameter by 5mm thick compacts. The characteristics of the SRS technique and the structural features of the shock synthesized products will be discussed. 18 refs., 11 figs.

There has been considerable work over the past few years to study shock-induced solid state chemistry. In the present report, issues raised in the area are reviewed and critical concepts are discussed. The distinctive nature of solid state chemistry compared to liquid and gas phase chemistry is emphasized and material probes suitable for the study of solids are described. In order for solids to react in times less than one microsecond, unusual processes must be initiated in shock compression. Chief among the unique shock processes is the mixing of reactants by the large kinetic energy of shock-compression pulses. Mixing and fluid-like flow can lead to sufficiently intimate contact between reactants to permit complete chemical reaction in the solid state on the time scale of the experiment. Shock-induced solid state chemistry may be described as an unusually intense mechanochemical process. 24 refs., 2 figs.