Interfacial Chemistry in Al/CuO Reactive Nanomaterial and Its Role in Exothermic Reaction.

Interface layers between reactive and energetic materials in nanolaminates or nanoenergetic materials are believed to play a crucial role in the properties of nanoenergetic systems. Typically, in the case of Metastable Interstitial Composite nanolaminates, the interface layer between the metal and oxide controls the onset reaction temperature, reaction kinetics, and stability at low temperature. So far, the formation of these interfacial layers is not well understood for lack of in situ characterization, leading to a poor control of important properties. We have combined in situ infrared spectroscopy and ex situ X-ray photoelectron spectroscopy, differential scanning calorimetry, and high resolution transmission electron microscopy, in conjunction with firstprinciples calculations to identify the stable configurations that can occur at the interface and determine the kinetic barriers for their formation. We find that (i) an interface layer formed during physical deposition of aluminum is composed of a mixture of Cu, O, and Al through Al penetration into CuO and constitutes a poor diffusion barrier (i.e., with spurious exothermic reactions at lower temperature), and in contrast, (ii) atomic layer deposition (ALD) of alumina layers using trimethylaluminum (TMA)produces a conformal coating that effectively prevents Al diffusion even for ultrathin layer thicknesses (∼0.5 nm), resulting in better stability at low temperature and reduced reactivity. Importantly, the initial reaction of TMA with CuO leads to the extraction of oxygen from CuO to form an amorphous interfacial layer that is an important component for superior protection properties of the interface and is responsible for the high system stability. Thus, while Al e-beam evaporation and ALD growth of an alumina layer on CuO both lead to CuO reduction, the mechanism for oxygen removal is different, directly affecting the resistance to Al diffusion. This work reveals that it is the nature of the monolayer interface between CuO and alumina/Al rather than the thickness of the alumina layer that controls the kinetics of Al diffusion, underscoring the importance of the chemical bonding at the interface in these energetic materials

Interfacial Reaction During High Energy Ball Milling Dispersion of Carbon Nanotubes into Ti6Al4V

The unique thermal and mechanical properties of carbon nanotubes (CNTs) have made them choice reinforcements for metal matrix composites (MMCs). However, there still remains a critical challenge in achieving homogeneous dispersion of CNTs in metallic matrices. Although high energy ball milling (HEBM) has been reported as an effective method of dispersing CNTs into metal matrices, a careful selection of the milling parameters is important not to compromise the structural integrity of CNTs which may cause interfacial reactions with the matrix. In this study, multi-walled carbon nanotubes (MWCNTs) were purified by annealing in argon and vacuum atmospheres at 1000 and 1800 °C, respectively, for 5 h to remove possible metallic catalyst impurities. Subsequently, 1, 2 and 3 wt.% MWCNTs were dispersed by adapted HEBM into Ti6Al4V alloy metal matrix. Raman spectroscopy (RS), x-ray diffraction, scanning electron microscopy, energy-dispersive x-ray spectrometry and transmission electron microscopy techniques were used to characterize the as-received and annealed MWCNTs, as well as the admixed MWCNT/Ti6Al4V nanocomposite powders. The experimental results showed that vacuum annealing successfully eliminated retained nickel (Ni) catalysts from MWCNTs, while the adapted HEBM method achieved a relative homogeneous dispersion of MWCNTs into the Ti6Al4V matrix and helped to control interfacial reactions between defective MWCNTs and the metal matrix

Oxidation of nano-sized aluminum powders

Oxidation of aluminum nanopowders obtained by electro-exploded wires is studied. Particle size distributions are obtained from transmission electron microscopy (TEM) images. Thermo-gravimetric (TG) experiments are complemented by TEM and XRD studies of partially oxidized particles. Qualitatively, oxidation follows the mechanism developed for coarser aluminum powder and resulting in formation of hollow oxide shells. Sintering of particles is also observed. The TG results are processed to account explicitly for the particle size distribution and spherical shapes, so that oxidation of particles of different sizes is characterized. The apparent activation energy is obtained as a function of the reaction progress using model-free isoconversion processing of experimental data. A complete phenomenological oxidation model is then proposed assuming a spherically symmetric geometry. The oxidation kinetics of aluminum powder is shown to be unaffected by particle sizes reduced down to tens of nm. The apparent activation energy describing growth of amorphous alumina is increasing at the very early stages of oxidation. The higher activation energy is likely associated with an increasing homogeneity in the growing amorphous oxide layer, initially containing multiple defects and imperfections. The trends describing changes in both activation energy and pre-exponent of the growing amorphous oxide are useful for predicting ignition delays of aluminum particles. The kinetic trends describing activation energies and pre-exponents in a broader range of the oxide thicknesses are useful for prediction of aging behavior of aluminum powders

Oxidation of nano-sized aluminum powders

Oxidation of aluminum nanopowders obtained by electro-exploded wires is studied. Particle size distributions are obtained from transmission electron microscopy (TEM) images. Thermo-gravimetric (TG) experiments are complemented by TEM and XRD studies of partially oxidized particles. Qualitatively, oxidation follows the mechanism developed for coarser aluminum powder and resulting in formation of hollow oxide shells. Sintering of particles is also observed. The TG results are processed to account explicitly for the particle size distribution and spherical shapes, so that oxidation of particles of different sizes is characterized. The apparent activation energy is obtained as a function of the reaction progress using model-free isoconversion processing of experimental data. A complete phenomenological oxidation model is then proposed assuming a spherically symmetric geometry. The oxidation kinetics of aluminum powder is shown to be unaffected by particle sizes reduced down to tens of nm. The apparent activation energy describing growth of amorphous alumina is increasing at the very early stages of oxidation. The higher activation energy is likely associated with an increasing homogeneity in the growing amorphous oxide layer, initially containing multiple defects and imperfections. The trends describing changes in both activation energy and pre-exponent of the growing amorphous oxide are useful for predicting ignition delays of aluminum particles. The kinetic trends describing activation energies and pre-exponents in a broader range of the oxide thicknesses are useful for prediction of aging behavior of aluminum powders