Search

Thermite multilayered films have the potential to be used as local high intensity heat sources for a variety of applications. Improving the ability of researchers to more rapidly develop Micro Electro Mechanical Systems devices based on thermite multilayer films requires predictive modeling in which an understanding of the relationship between the properties (ignition and flame propagation), the multilayer structure and composition (bilayer thicknesses, ratio of reactants, and nature of interfaces), and aspects related to integration (substrate conductivity and ignition apparatus) is achieved. Assembling all these aspects, this work proposes an original 2D diffusion-reaction modeling framework to predict the ignition threshold and reaction dynamics of Al/CuO multilayered thin films. This model takes into consideration that CuO first decomposes into Cu2O, and then, released oxygen diffuses across the Cu2O and Al2 O3 layers before reacting with pure Al to form Al2O3. This model is experimentally validated from ignition and flame velocity data acquired on Al/CuO multilayers deposited on a Kapton layer. This paper discusses, for the first time, the importance of determining the ceiling temperature above which the multilayers disintegrate, possibly before their complete combustion, thus severely impacting the reaction front velocity and energy release. This work provides a set of heating surface areas to obtain the best ignition conditions, i.e., with minimal ignition power, as a function of the substrate type. [ABSTRACT FROM AUTHOR]

The ignition of the Al/CuO multilayered material is studied experimentally to explore the effects of the heating surface area, layering, and film thickness on the ignition characteristics and reaction performances. After the description of the micro-initiator devices and ignition conditions, we show that the heating surface area must be properly calibrated to optimize the nanothermite ignition performances. We demonstrated experimentally that a heating surface area of 0.25 mm2 is sufficient to ignite a multilayered thermite film of 1.6 mm wide by a few cm long, with a success rate of 100%. A new analytical and phenomenological ignition model based on atomic diffusion across layers and thermal exchange is also proposed. This model considers that CuO first decomposes into Cu2O, and then the oxygen diffuses across the Cu2O and Al2O3layers before reaching the Al layer, where it reacts to form Al2O3. The theoretical results in terms of ignition response times confirm the experimental observation. The increase of the heating surface area leads to an increase of the ignition response time and ignition power threshold (go/no go condition). We also provide evidence that, for any heating surface area, the ignition time rapidly decreases when the electrical power density increases until an asymptotic value. This time point is referred to as the minimum response ignition time, which is a characteristic of the multilayered thermite itself. At the stoichiometric ratio (Al thickness is half of the CuO thickness), the minimum ignition response time can be easily tuned from 59 μs to 418 ms by tuning the heating surface area. The minimum ignition response time increases when the bilayer thickness increases. This work not only provides a set of micro-initiator design rules to obtain the best ignition conditions and reaction performances but also details a reliable and robust MicroElectroMechanical Systems process to fabricate igniters and brings new understanding of phenomena governing the ignition process of Al/CuO multilayers. [ABSTRACT FROM AUTHOR]

Sputter-deposited Al/CuO multilayers capable of highly energetic reactions have been the subject of intense studies for tunable initiation and actuation. Designing high performance Al/CuO-based initiator devices definitively requires reliable prediction of their ignition and reaction kinetics including self-heating or ageing as a function of heating rate and environmental conditions. The paper proposes a heterogeneous reaction model integrating an ensemble of basic mechanisms (oxygen diffusion, structural transformations, polymorphic phase changes) that have been collected from recent experimental investigations. The reaction model assumes that the rate of reaction is limited by the transport of oxygen across the growing layer of Al2O3 separating Al and CuO. Importantly, we show that the model predicts reasonably all exotherms through a wide range of temperature (ambient – 1000°C), all resulting from a pure diffusion process as experimentally observed for such Al/CuO multilayers. The model shows how the temperature ramp affects the structure of the multilayer and especially the growth of alumina-based interfacial regions. It highlights the importance of the interfacial chemistry evolution such as the native mixture of AlxCuyOz transformation into a thin amorphous alumina, and the polymorphic phase transformation of this latter. The first one occurring at ∼350°C results in a loss of continuity of the interface leading to the accelerated redox reaction whereas the second one occurring between 500 and 600°C produces a denser barrier to oxygen diffusion leading to the stop of redox reaction. We finally use the model to simulate thermal annealing as usually performed in accelerated ageing experiments. We theoretically observe and experimentally validate that a two weeks exposure of the multilayers at 200°C starts degrading the multilayers thermal properties whereas when the temperature remains below 200°C, the material keeps its entire integrity. [ABSTRACT FROM AUTHOR]

[Display omitted] • First thermokinetic study on Aluminized nanothermites to predict their aging and shelf-life. • Certain annealing conditions boost the combustion performance while sacrificing heat reservoir. • Al based thermites are thermally stable for one century until 200 °C. • Al/oxide interface chemistry has more impact on the reactivity than reaction progress evolution. We examine the thermal aging of four Al based thermites chosen among the most commonly used in microenergetic systems: Al/CuO, Al/Fe 2 O 3 , Al/Fe 3 O 4 and Al/Co 3 O 4. For each nanothermite system, we applied the modified Friedmann isoconversional method from DSC signals to calculate the kinetic parameters of reactions and the function of the reaction progress in air and argon. As result, it is found that all thermites should be thermally stable for one century when stored at temperatures below 200 °C, except for Al/Fe 3 O 4 which readily converts into Al/Fe 2 O 3 before the thermite reaction onset. Then, we designed annealing experiments to a fixed reaction progress : (i) as simulated after 100 years storage at the ambient temperature, (ii) up to 5%. The pressure development and burning rate of aged thermites are compared with as-prepared ones. After annealing at 200 °C in air and 400 °C in argon, an unforeseen faster reaction and pressurization rates are observed for Al/CuO and Al/Fe 2 O 3 thermites. STEM and EDX show that the annealing provokes a modification of the aluminum particles structure accompanied with a softening of the alumina which explains the enhanced pressure performances and burn rates. Whereas the same nanothermites, Al/CuO and Al/Fe 2 O 3 , annealed at 400 °C in air, feature a reduced reactivity due to the over-oxidations of the aluminum core and the formation of crystalline alumina shell. These results reveal the high complexity of aging processes in powdered nanothermites as it provokes, not only a consumption of the heat reservoir, but also a modification of the Al/oxidizer interface morphology and chemistry which has a greater impact on the material reactivity than cumulative heat release and reaction progress evolution. [ABSTRACT FROM AUTHOR]

The complex Al/CuO self-propagating reaction involving multi-phase and multi-species dynamics was studied in order to investigate the very high flame temperature around the vaporization temperature of alumina, even under a neutral environment. Experiments were performed on different sputter-deposited Al/CuO multilayers coupling optical spectroscopy with high speed camera measurements. The clear presence of both AlO and Al signatures in gas phase suggests that the redox reaction starts in the bulk nanolaminate, which then rapidly tear off the substrate to continue burning in a heterogeneous (condensed and gas) phase in the environment. The flame temperature increases with the stoichiometry but is independent of the bilayer thickness. In addition to the confirmation of the effects of stoichiometry and the bilayer thickness on the characteristics of the self-propagating reaction, the predominant role of process-induced residual stress was highlighted for the first time; it can lead to an early disruption of the multilayer long before the completion of the redox reaction. [ABSTRACT FROM AUTHOR]