3D printing of reactive materials has, to date, primarily focused on controlling reaction velocities and energy release rates by printing novel architectures, which during reaction typically form gaseous and oxide powder products. The utility of printed reactive materials can be increased by designing the material such that its reaction produces both a controlled energy release and a functional product phase without gaseous products. Here, we report the direct ink writing of reactive materials composed of ternary nanocomposite powders that exhibit gasless, exceptionally low velocity reactions. The printed features can be patterned in arbitrary form factors and are brittle and electrically insulating as‐printed. Using a self‐propagating synthesis reaction, these features can be transformed into a mechanically robust, electrically conductive cermet that is capable of handling high currents. This study provides a new paradigm for printing multifunctional reactive materials in which both the energy release of the reaction, as well as the reaction products themselves, are useful for potential applications ranging from printed electronic devices to controlled, directed energy release.
Nucleation, the initial formation of a new phase from a parent phase, plays an important role in the eventual microstructure and properties of materials. Theories and models of nucleation have been integral to materials science for close to a century. These models assume that the parent material is compositionally homogeneous on length-scales relevant to nucleation. However, in certain materials – such as thin films or reactive nanolaminates – sharp gradients in the composition may influence nucleation. Models and theories exploring these impacts are based on little direct experimental data. Here we present means of producing and characterizing samples with composition gradients to measure the impacts of gradients on nucleation. We fabricate amorphous Cu-Zr films with known composition gradients through their thicknesses; we perform isochronal nanocalorimetry to measure the impact of the gradients on nucleation and growth; and we characterize the samples before and after reaction. We see evidence of phase separation of the vapor-quenched Cu-Zr amorphous films. While we measure differences between the samples with gradients and those without, the gradients relax sufficiently during heating such that nucleation (the onset of crystallization) occurs at the same temperatures. For both sets of samples we find three distinct regions of heat release: the first we attribute to local ordering, the second to extended phase separation and interdiffusion, and the third to nucleation and growth of the Cu10Zr7 crystalline phase. This work represents a first step towards investigating the impact of gradients on nucleation, as well as growth.
We have developed an improved method of time-resolved x-ray reflectivity (XRR) using monochromatic synchrotron radiation. Our method utilizes a polycapillary x-ray optic to create a range of incident angles and an area detector to collect the specular reflections. By rotating the sample normal out of the plane of the incident fan, we can separate the surface diffuse scatter from the reflectivity signal, greatly improving the quality of the XRR spectra compared to previous implementations. We demonstrate the time-resolved capabilities of this system, with temporal resolution as low as 10 ms, by measuring XRR during the annealing of Al/Ni nano-scale multilayers and use this information to extract the activation energy for interdiffusion in this system. a) hj335@cornell.edu 1
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