Publications

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Nanocrystalline metals offer significant improvements in structural performance over conventional alloys. However, their performance is limited by grain boundary instability and limited ductility. Solute segregation has been proposed as a stabilization mechanism, however the solute atoms can embrittle grain boundaries and further degrade the toughness. In the present study, we confirm the embrittling effect of solute segregation in Pt–Au alloys. However, more importantly, we show that inhomogeneous chemical segregation to the grain boundary can lead to a new toughening mechanism termed compositional crack arrest. Energy dissipation is facilitated by the formation of nanocrack networks formed when cracks arrested at regions of the grain boundaries that were starved in the embrittling element. This mechanism, in concert with triple junction crack arrest, provides pathways to optimize both thermal stability and energy dissipation. A combination of in situ tensile deformation experiments and molecular dynamics simulations elucidate both the embrittling and toughening processes that can occur as a function of solute content.

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The different rate-limiting processes underlying ignition and self-propagating reactions in Al/Pt multilayers are examined through experiments and analytical modeling. Freestanding, ∼1.6 μm-thick Al/Pt multilayers of varied stoichiometries and nanometer-scale layer thicknesses ignite at temperatures below the melting point of both reactants (and eutectics) demonstrating that initiation occurs via solid-state mixing. Equimolar multilayers exhibit the lowest ignition temperatures when comparing structures having a specific bilayer thickness. An activation energy of 76.6 kJ/mol at. associated with solid state mass transport is determined from the model analysis of ignition. High speed videography shows that equimolar Al/Pt multilayers undergo the most rapid self-sustained reactions with wavefront speeds as large as 73 m/s. Al- and Pt-rich multilayers react at reduced rates (as low as 0.3 m/s), consistent with reduced heat of reaction and lower adiabatic temperatures. An analytical model that accounts for key thermodynamic properties, preliminary mixing along interfaces, thermal transport, and mass diffusion is used to predict the wavefront speed dependencies on bilayer thickness. Good fits to experimental data provide estimates for activation energy (51 kJ/mol at.) associated with mass transport subject to high heating rates and thermal diffusion coefficient of premixed interfacial volumes (2.8 × 10-6 m2/s). Pt dissolution into molten Al is identified as a rate-limiting step underlying high temperature propagating reactions in Al/Pt multilayers.

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Recent work suggests that thermally stable nanocrystallinity in metals is achievable in several binary alloys by modifying grain boundary energies via solute segregation. The remarkable thermal stability of these alloys has been demonstrated in recent reports, with many alloys exhibiting negligible grain growth during prolonged exposure to near-melting temperatures. Pt–Au, a proposed stable alloy consisting of two noble metals, is shown to exhibit extraordinary resistance to wear. Ultralow wear rates, less than a monolayer of material removed per sliding pass, are measured for Pt–Au thin films at a maximum Hertz contact stress of up to 1.1 GPa. This is the first instance of an all-metallic material exhibiting a specific wear rate on the order of 10−9 mm3 N−1 m−1, comparable to diamond-like carbon (DLC) and sapphire. Remarkably, the wear rate of sapphire and silicon nitride probes used in wear experiments are either higher or comparable to that of the Pt–Au alloy, despite the substantially higher hardness of the ceramic probe materials. High-resolution microscopy shows negligible surface microstructural evolution in the wear tracks after 100k sliding passes. Mitigation of fatigue-driven delamination enables a transition to wear by atomic attrition, a regime previously limited to highly wear-resistant materials such as DLC.

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Direct laser irradiation of sputter deposited Al/Pt nanolaminate multilayers results in rapid local heating and exothermic mixing of reactant layers. Milli- and microsecond pulsed laser irradiation under certain test conditions leads to single-point ignition of rapid, self-propagating, formation reactions. Multilayers having bilayer thicknesses of 328 nm, 164 nm, and 65 nm are characterized by their ignition onset times and temperatures. Smaller bilayer thickness multilayers require less laser intensity for ignition compared with larger bilayer designs (when utilizing a particular pulse duration). The relationship between laser intensity and ignition onset time is used to calibrate an activation energy for ignition within a finite element reactive heat transport model. The local heating rate is varied from 104 K/s to 106 K/s by selecting a laser intensity. Kissinger analysis was performed on the heating rate-dependent ignition temperatures measured with high speed pyrometry to experimentally determine an activation energy in the foils of (6.2 ± 1.6 × 104 J/mole atoms). This value is then compared to an activation energy produced from model fits to an ignition onset time of 7.2 × 104 J/mole atoms.

For this study, diamond-like carbon (DLC) films were tribochemically formed from ambient hydrocarbons on the surface of a highly stable nanocrystalline Pt-Au alloy. A sliding contact between an alumina sphere and Pt-Au coated steel exhibited friction coefficients as low as μ = 0.01 after dry sliding in environments containing trace (ppb) organics. Ex situ analysis indicated that the change in friction coefficient was due to the formation of amorphous carbon films, and Raman spectroscopy and elastic recoil analysis showed that these films consist of sp²/sp³ amorphous carbon with as much as 20% hydrogen. Transmission electron microscopy indicated these films had thicknesses exceeding 100 nm, and were enhanced by the incorporation of worn Pt-Au nanoparticles. The result was highly wear-resistant, low-friction DLC/Pt-Au nanocomposites. Atomistic simulations of hydrocarbons under shear between rigid Pt slabs using a reactive force field showed stress-induced changes in bonding through chain scission, a likely route towards the formation of these coatings. This novel demonstration of in situ tribochemical formation of self-lubricating films has significant impact potential in a wide range of engineering applications.

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A diffusion-limited reaction model was calibrated for Al/Pt multilayers ignited on oxidized silicon, sapphire, and tungsten substrates, as well as for some Al/Pt multilayers ignited as free-standing foils. The model was implemented in a finite element analysis code and used to match experimental burn front velocity data collected from several years of testing at Sandia National Laboratories. Moreover, both the simulations and experiments reveal well-defined quench limits in the total Al + Pt layer (i.e., bilayer) thickness. At these limits, the heat generated from atomic diffusion is insufficient to support a self-propagating wave front on top of the substrates. Quench limits for reactive multilayers are seldom reported and are found to depend on the thermal properties of the individual layers. Here, the diffusion-limited reaction model is generalized to allow for temperature- and composition-dependent material properties, phase change, and anisotropic thermal conductivity. Utilizing this increase in model fidelity, excellent overall agreement is shown between the simulations and experimental results with a single calibrated parameter set. However, the burn front velocities of Al/Pt multilayers ignited on tungsten substrates are over-predicted. Possible sources of error are discussed and a higher activation energy (from 41.9 kJ/mol.at. to 47.5 kJ/mol.at.) is shown to bring the simulations into agreement with the velocity data observed on tungsten substrates. This higher activation energy suggests an inhibited diffusion mechanism present at lower heating rates.

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