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Nanoenergetic materials are beginning to play an important role in part because they are being considered as energetic components for materials, chemical, and biochemical communities (e.g., microthermal sources, microactuators, in situ welding and soldering, local enhancement of chemical reactions, nanosterilization, and controlled cell apoptosis) and because their fabrication/synthesis raises fundamental challenges that are pushing the engineering and scientific frontiers. One such challenge is the development of processes to control and enhance the reactivity of materials such as energetics of nanolaminates, and the understanding of associated mechanisms. We present here a new method to substantially decrease the reaction onset temperature and in consequence the reactivity of nanolaminates based on the incorporation of a Cu nanolayer at the interfaces of Al/CuO nanolaminates. We further demonstrate that control of its thickness allows accurate tuning of both the thermal transport and energetic properties of the system. Using high resolution transmission electron microscopy, X-ray diffraction, and differential scanning calorimetry to analyze the physical, chemical and thermal characteristics of the resulting Al/CuO + interfacial Cu nanolaminates, we find that the incorporation of 5 nm Cu at both Al/CuO and CuO/Al interfaces lowers the onset temperature from 550 to 475 °C because of the lower-temperature formation of Al-Cu intermetallic phases and alloying. Cu intermixing is different in the CuO/Cu/Al and Al/Cu/CuO interfaces and independent of total Cu thickness: Cu readily penetrates into Al grains upon annealing to 300 °C, leading to Al/Cu phase transformations, while Al does not penetrate into Cu. Importantly, θ-Al2Cu nanocrystals are created below 63% wt Cu/Al, and coexist with the Al solid solution phase. These well-defined θ-Al2Cu nanocrystals seem to act as embedded Al+CuO energetic reaction triggers that lower the onset temperature. We show that ∼10 nm thick Cu at Al/CuO interfaces constitutes the optimum amount to increase both reactivity and overall heat of reaction by a factor of ∼20%. Above this amount, there is a rapid decrease of the heat of reaction.
Al/CuO energetic structure are attractive materials due to their high thermal output and propensity to produce gas. They are widely used to bond components or as next generation of MEMS igniters. In such systems, the reaction process is largely dominated by the outward migration of oxygen atoms from the CuO matrix toward the aluminum layers, and many recent studies have already demonstrated that the interfacial nanolayer between the two reactive layers plays a major role in the material properties. Here we demonstrate that the ALD deposition of a thin ZnO layer on the CuO prior to Al deposition (by sputtering) leads to a substantial increase in the efficiency of the overall reaction. The CuO/ZnO/Al foils generate 98% of their theoretical enthalpy within a single reaction at 900 °C, whereas conventional ZnO-free CuO/Al foils produce only 78% of their theoretical enthalpy, distributed over two distinct reaction steps at 550 °C and 850 °C. Combining high-resolution transmission electron microscopy, X-ray diffraction, and differential scanning calorimetry, we characterized the successive formation of a thin zinc aluminate (ZnAlO) and zinc oxide interfacial layers, which act as an effective barrier layer against oxygen diffusion at low temperature.
The integration of high-purity nano-objects on substrates remains a great challenge for addressing scaling-up issues in nanotechnology. For instance, grafting gold nanoparticles (NPs) on zinc oxide films, a major step process for catalysis or photovoltaic applications, still remains difficult to master. We report a modified photodeposition (P-D) approach that achieves tight control of the NPs size (7.5 ± 3 nm), shape (spherical), purity, and high areal density (3500 ± 10 NPs/μm) on ZnO films. This deposition method is also compatible with large ZnO surface areas. Combining electronic microscopy and X-ray photoelectron spectroscopy measurements, we demonstrate that growth occurs primarily in confined spaces (between the grains of the ZnO film), resulting in gold NPs embedded within the ZnO surface grains thus establishing a unique NPs/surface arrangement. This modified P-D process offers a powerful method to control nanoparticle morphology and areal density and to achieve strong Au interaction with the metal oxide substrate. This work also highlights the key role of ZnO surface morphology to control the NPs density and their size distribution. Furthermore, we experimentally demonstrate an increase of the ZnO photocatalytic activity due to high densities of Au NPs, opening applications for the decontamination of water or the photoreduction of water for hydrogen production.
Deposition
of Al on ZnO is used for a number of electronic and
catalytic devices as well as for nanoenergetic materials. The interface
structure and chemical composition often control the performance of
devices. In this study, in situ infrared spectroscopy, X-ray photoemission
spectroscopy, and low energy ion scattering are combined to investigate
the initial stage of interface formation between Al and ZnO. We find
that (a) the interface is highly inhomogeneous with discontinuous
Al patches, leaving ∼10% of the ZnO surface uncovered even
after deposition of an equivalent of 11 nm-thick Al film; (b) upon
Al deposition, Al reduces ZnO by forming Al2O3 and releasing Zn to the surface, and this process continues as more
Al is deposited; (c) the reduced surface Zn atoms readily desorb at
150 °C; and (d) at higher temperature (>600 °C) all Al
is
oxidized as a result of mass transport. Deposition of a thin Al2O3 layer on ZnO prior to Al deposition effectively
prevents Al penetration and Zn release, requiring higher temperatures
to oxidize Al.
The cladding welding analysis with pulsed flux cored arc welding (FCAW) process, were carried over a AISI 1020 base metal (thickness 12,7 mm, width 63,5 and length 185mm) with an CA6NM steel wire with diameter of 1.2mm. Was performed only one weld cord in the flat position. For experimental design was used the method of Taguchi L9 to determinate the parameter to be analyzed through the application of the analysis of variance (ANOVA) method. The response signals in RMS (Root Mean Square) analyzed were the voltage, current and acceleration. The procedure is based on a non-parametric domain-selective ANOVA for functional data, which results in the selection of the intervals of the domain presenting the most statistically significant effects of each factor over the selected response signals. The statistical results presented by ANOVA show that not all the selected variables have influenced the results. The best results for the cladding welding were obtained from the current average of230amperes, and statistically the average current was the variable that significantly affected the results, however, the welding speed only affected the yield of the process.
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