Reactive Multilayer Research Articles

Nanojoining of TiAl with Ni-Al Reactive Multilayer Nanofoils: A Molecular Dynamics Study

Nanojoining of TiAl with Ni-Al Reactive Multilayer Nanofoils: A Molecular Dynamics Study

2D Computational Fluid Dynamics Simulation Analysis of the Assembly of Low‐Temperature Cofired Ceramics/Low‐Temperature Cofired Ceramics and Si/Si Sandwiches by Reactive Bonding

Numerical computational fluid dynamics simulations have been performed on 2D sandwich models to compare the performance of low‐temperature cofired ceramics (LTCC)/LTCC and Si/Si sandwiches used in reactive bonding. In the sandwich model layers of solder, silver and a reactive multilayer used to bond the substrates are modeled. Additional to this, the surrounding air environment is also modeled. For simulating the heat released by the multilayer system, a user‐defined function in the form of a square wave is written for the heat source with a defined width, corresponding to the reaction width, and this propagates at a fixed speed. Two sandwiches, one with LTCC/LTCC, and the other with Si/Si, are simulated and their response analyzed in terms of the solidification/melting of the solder and their respective time–temperature histories.

Effects of Intermetallic Phase Formation and Bilayer Spacing on the Oxygen Exchange Process in Mg–CuO Reactive Multilayer Films

Effects of Intermetallic Phase Formation and Bilayer Spacing on the Oxygen Exchange Process in Mg–CuO Reactive Multilayer Films

Molecular Dynamics Analysis of Impact of Alloyed Interlayers in Ni–Al Reactive Multilayer Nanofoils

Molecular Dynamics Analysis of Impact of Alloyed Interlayers in Ni–Al Reactive Multilayer Nanofoils

Enhancing Ni–Ti shape memory alloy diffusion bonding with Ti/Ni reactive multilayer foils

This study investigates the utilization of Ti/Ni reactive multilayer foils as an energy source for facilitating the joining of Ni–Ti shape memory alloys through diffusion bonding. Multilayered samples were prepared using a 10-cycle accumulative roll bonding (ARB) process to be used for the bonding process. Diffusion bonding employing reactive multilayers was conducted over a temperature range of 600 °C to 900 °C, at 5 MPa pressure, with a 1-h hold time. Additionally, a comparison was made with a diffusion-bonded Nitinol sample at 900 °C without a reactive multilayer. Materials characterization and testing involved scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), shear strength testing, and differential scanning calorimetry (DSC), which were conducted on the bonded samples. The findings underscored the advantages of using reactive multilayers for diffusion bonding. These benefits included the formation of TiNi and the induction of a shape memory effect in the joint region, alongside a 1.5 times shear strength compared to identical diffusion bonding conditions without reactive multilayers. Moreover, employing reactive multilayers in the diffusion bonding of Nitinol holds promise for significantly reducing the energy needed to achieve robust and seamless bonded boundaries in the joining area.

Electroplating of Palladium‐Based Integrated Reactive Multilayer Systems (iRMS)

Bonding with integrated reactive material systems enables joining of heterogeneous substrates at room temperature. The increasing diversity of electronic modules raises the demand for low temperature bonding processes for heat sensitive components. In this article, fundamental steps for the deposition of Pd/In multilayers from a single bath electrolyte are presented. It furthermore describes the deposition of Pd/Sn reactive multilayers for bonding application on ceramic substrates and introduces a new semi‐automated plating tool for Pd/Sn multilayers. The Pd/Sn multilayers can be deposited reproducible on silicon and ceramic substrates. While a bilayer period of 425 nm enables stable ignition and bonding of Si substrates, the bilayer period for ceramics has to be increased to 620 nm to compensate the higher heat dissipation into the substrate. By integrating 2.5–9 μm thick Sn compensation layers beneath the integrated reactive multilayer systems (iRMS) to smoothen the surface profile of the printed metallization and improved bonding processes with wedge compensation, a homogeneous bond along the whole interface can be achieved.

Simulation of Heat Transfer and Propagation Velocity for Different Heat Loss Conditions for Guided Propagation Fronts in Reactive Multilayer Foils

Engineering self‐propagating reactions in reactive material systems requires an understanding of critical ignition and propagation conditions. These conditions are governed by the material properties of the reactive materials responsible for net heat generation, as well as by external environmental conditions that primarily determine net heat loss. In this study, it is aimed to utilize a numerical model to investigate the critical conditions for reaction propagation based solely on the heat‐transfer equation, enabling thorough examination with significantly low computational effort. Comparing simulations with experiments demonstrates a high level of agreement in predicting reaction propagation. Additionally, this numerical model provides valuable information regarding heat distribution in substrate materials.

Investigating the reaction mechanism of zirconium as a fuel in reactive multilayer films via multimodal analysis

In this report, we examine the intricate details of the mechanism driving Zr/CuO thermite system, shedding new light on the exceptional reactivity of Zr fuel with oxygen. Magnetron-sputtered Zr/CuO reactive multilayers were deposited, and thermo-physical techniques were employed to characterize the progression of the chemical reaction upon heating. Unlike commonly used Al fuel, Zr/CuO exhibited 100% heat release below 500 °C, contrasting with the ∼5% observed for conventional Al/CuO system. This enhanced reactivity at low temperature is attributed to the rapid oxygen consumption behavior of Zr, due to the poor barrier of ZrOx to oxygen diffusion. The oxidizing behavior of Zr was quantitatively analyzed using electron microscopy and spectroscopy. Our observations reveal a three-step process of Zr oxidation facilitated by a rapid reduction of CuO to metallic Cu accompanied by the formation of an intermediate Cu2O phase: (i) a preliminary low-temperature mass transport initiating at 275 °C, (ii) partial Zr oxidation forming ZrO2 and oxygen enriched Zr and finally (iii) complete conversion to zirconia at 450 °C. Finally, Zr/CuO reactive thin-films demonstrated a very high reactivity with an ignition delay time of 0.04 ± 0.016 ms and a burn rate of 3.5 m.s−1, in stark contrast to the same volume of Al/CuO, which failed to ignite and burn altogether. This study not only deepens our comprehension of Zr-based thermite system but also underscores its potential for diverse applications in energetic materials.

Mechanical Ignition of Al/Ni Reactive Multilayer Systems: Influence of Impacting Material, Its Properties, and Geometric Characteristics

Mechanical Ignition of Al/Ni Reactive Multilayer Systems: Influence of Impacting Material, Its Properties, and Geometric Characteristics

Controlling Propagation Velocity in Al/Ni Reactive Multilayer Systems by Periodic 2D Surface Structuring

The chemical energy released as heat during the exothermic reaction of reactive multilayer systems has shown potential applications in various technological areas, e.g., in joining applications. However, controlling the heat release rate and the propagation velocity of the reaction is required to enhance their performance in most of these applications. Herein, a method to control the propagation velocity and heat release rate of the system is presented. The sputtering of Al/Ni multilayers on substrates with periodic 2D surface structures promotes the formation of growth defects into the system. This modification in the morphology locally influences the reaction characteristics. Tailoring the number of 2D structures in the substrate enables the control of the velocity and maximum temperature of the propagation front. The morphology of the produced reactive multilayers is investigated before and after reaction using scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. In addition, the enthalpy of the system is obtained through calorimetric analysis. The self‐sustained and self‐propagating reaction of the systems is monitored by a high‐speed camera and a high‐speed pyrometer, thus revealing the propagation velocity and the temperatures with time resolution in the microsecond regime.

Influence of Oxide Formation Following Ultrashort Pulsed Laser Micromachining on Self‐Propagating Reactions in Free‐Standing Ni/Al Reactive Multilayer Foils

Reactive metallic multilayers, renowned for their exothermic self‐propagating reactions, show a distinct ability to achieve minimal thermal influence in processes such as welding and soldering, where minimizing the thermal impact on the material being joined is crucial. Ultrashort pulsed lasers offer precision micromachining with negligible thermal damage, making them ideal for processing such sensitive materials. However, the formation and redeposition of oxide phases is a commonly observed side effect, especially when structuring in ambient air. This study investigates the effects of oxide formed after femtosecond laser treatment on self‐propagating properties, including propagation velocity and microstructure of Ni/Al reactive multilayer foils. Samples with varied line spacings between laser‐cut trenches are created. Scanning electron microscopy, high‐speed camera videography, and image analysis are employed to analyze the microstructure and quantify velocities. Thermal simulations enhance the understanding of the oxide's role in self‐propagating dynamics. The findings suggest that even a small oxide layer significantly decelerates the self‐propagating reaction. The oxide functions as a thermal ballast by absorbing the thermal energy generated during the reaction, without actively participating in the reaction mechanism.

Reactive Ti/Ni multilayer composites produced via accumulative roll-bonding (ARB): post-annealing treatment

ABSTRACT Ti/Ni multilayers, produced through the accumulative-roll bonding (ARB) process, serve as reactive multilayer, capturing energy to optimize manufacturing processes and contribute to TiNi (shape memory alloy) production. This research specifically examines the impact of the number of layers on microstructural and thermal properties after activation through heating. Energy-dispersive spectroscopy (EDS), field emission scanning electronmicroscopy (FESEM), and differential scanning calorimeter (DSC) were employed to analyse samples subjected to various ARB cycles. The findings indicate that in low-cycle ARB processing, the interdiffusion of Ni and Ti under normal conditions initiates the production of a very thin layer of TiNi at 800 °C, requiring extended holding times for increased thickness. Conversely, the formation of intermetallic compounds, particularly TiNi, and diffusion in high-cycle ARB-processed composites are accelerated. According to the DSC results, complete activation and phase transformation, accompanied by the release of energy (43–50 kJ/mol), occur at approximately 500–525°C without the need for any holding time. Consequently, for achieving a uniform TiNi phase, heat treatment of high-cycle ARB-processed composites up to 800°C – a temperature surpassing the activation temperature – without any holding time can be effectively employed.

Controlling reaction transfer between Al/Ni reactive multilayer elements on substrates

Reactive multilayers produce exothermic reaction with definite velocity and maximum temperature after ignition, which are the fundamental properties of the reactive multilayer systems. The generated heat with certain velocity makes it widely used in joining, bonding in the packaging, thermal batteries and many more applications. In this work, a distinct approach for achieving a reaction transfer between the reactive multilayers and different materials is demonstrated which can affect the generated temperature and velocity from the self-propagating properties of the reaction. For these intensions, we fabricated the Al/Ni reactive elements with certain separations between elements which allow to observe the reaction front transfer and emitted temperature in the reaction chain. The created separation between reactive elements are periodical and ordered systems with different thermal conductive properties. The temperature and definite velocity were measured by time-resolved pyrometer and high-speed camera measurements. SEM analysis showed the characteristics of the reaction transfer between reactive multilayer elements. It is predicted that: (I) The reaction front stops at a space with critical length; (II) Reducing heat loss through the substrate supports reaction front propagation through spaces; (III) Thermal property design of the spaces between the reactive elements enables property modification of the self-propagating reaction.Graphical abstract

Ni/Al multilayer reactions on nanostructured silicon substrates

Fast energy release, which is a fundamental property of reactive multilayer systems, can be used in a wide field of applications. For most applications, a self-propagating reaction and adhesion between the multilayers and substrate are necessary. In this work, a distinct approach for achieving self-propagating reactions and adhesion between deposited Ni/Al reactive multilayers and silicon substrate is demonstrated. The silicon surface consists of random structures, referred to as silicon grass, which were created by deep reactive ion etching. Using the etching process, structure units of heights between 8 and 13 µm and density between 0.5 and 3.5 structures per µm2 were formed. Ni and Al layers were alternatingly deposited in the stoichiometric ratio of 1:1 using sputtering, to achieve a total thickness of 5 µm. The analysis of the reaction and phase transformation was done with high-speed camera, high-speed pyrometer, and X-ray diffractometer. Cross-sectional analysis showed that the multilayers grew only on top of the silicon grass in the form of inversed cones, which enabled adhesion between the silicon grass and the reacted multilayers. A self-propagating reaction on silicon grass was achieved, due to the thermally isolating air pockets present around these multilayer cones. The velocity and temperature of the reaction varied according to the structure morphology. The reaction parameters decreased with increasing height and decreasing density of the structures. To analyze the exact influence of the morphology, further investigations are needed.

Influence of extrinsic induced tensile stress on the self-propagating high-temperature synthesis of nanosized Al/Ni multilayers

Reactive multilayer systems consisting of alternating nanoscale Al and Ni layers are applicable in joining, various pyrotechnic applications and thermal batteries. Since diffusion based high-temperature synthesis occurs without the presence of air, efforts have focused on investigating the understanding of the fundamental reaction processes and characteristics. The aim of this study is to expose the reactive multilayers to extrinsic induced tensile stress so that the self-propagating synthesis can proceed under these conditions. Further, the properties during and after the reaction will be investigated. Multilayers deposited by sputtering on Kapton® substrates with different bilayer– and total thicknesses as well as commercial Nanofoils® with thicknesses of 40 µm and 60 µm were used as samples. The investigations focused on the propagation velocity measured with a high-speed camera, the temperature regime determined with a high-speed pyrometer, and the formed phases after the synthesis examined via X-ray diffraction. The gained results of this study reveal important insights for the application of the reactive Al/Ni multilayer system in terms of stability or reliability related to propagation front velocity, maximum temperature and formed phases under induced external tensile stresses.Graphical abstract

Effects of Ultrashort Pulsed Direct Laser Writing on Ni/Al Reactive Multilayer Foils

Reactive multilayer foils (RMFs) for joining processes have attracted a great deal of attention over the last few years. They are capable of exothermic self-propagating reactions and can serve as localized heat sources for joining applications when ignited by suitable means. Using short and ultrashort pulsed lasers with carefully selected parameters, cutting and shaping of RMFs makes it possible to tailor heat release characteristics without triggering the reaction. The present study is an investigation of microstructural changes induced by femtosecond laser machining of a commercially available Ni/Al-based RMF. The effects of the specific laser parameters pulse duration and repetition rate on the heat-affected zone (HAZ) are investigated by scanning and transmission electron microscopy. Debris consisting of oxide deposits can be found at a distance of several tens of microns from the cut edge. A negligible HAZ extending to less than 100 nm was observed for all parameters tested and no signs of ignition of a self-propagating reaction were observed. These results underline the suitability of femtosecond lasers for metal machining with minimal heat input.

Microstructural Characterization and Self‐Propagation Properties of Reactive Al/Ni Multilayers Deposited onto Wavelike Surface Morphologies: Influence on the Propagation Front Velocity

Reactive multilayer systems are nanostructures of great interest for various technological applications because of their high energy release rate during the self‐propagating reaction of their components. Therefore, many efforts are aimed at controlling the propagation velocity of these reactions. Herein, reactive multilayer systems of Al/Ni in the shape of free‐standing foils with a wavelike surface morphology prepared by using sacrificial substrates with well‐aligned waves are presented and the propagation of the reaction along different directions of the reproduced waves is analyzed. During the ignition test, the propagation front is recorded with a high‐speed camera, and the maximum temperature is measured using a pyrometer. The propagation of the reaction is favored in the direction of the waves, which points out the influence of the anisotropy generated by this morphology and how it affects the propagation dynamics and the resulting microstructure. Furthermore, compared to their counterparts fabricated on flat substrates, these reactive multilayers with wavelike morphology exhibit a remarkable reduction in the propagation velocity of the reaction of about 50%, without significantly affecting the maximum temperature registered during the reaction.

Control of Large‐Scale Single‐Phase Ni Silicide Formation from Reactive Multilayers

The Ni/Si reactive multilayer (RML) is full of application potentials including reactive joining, igniters, and power sources. Here, the Ni/Si RMLs with atomic ratios of Ni and Si (2:1, 1:1, and 1:2) are studied, where the bilayer thickness and the total thickness are controlled to be 53 nm and 2 μm, respectively. After laser ignition, a rapid explosive reaction is observed where there are two self‐propagation wavefronts and their velocities reach 7.20 and 11.93 m s−1. The uniform, small grains, and single‐phase Ni silicides are obtained and controlled by tuning growth parameters. From the understanding of the Gibbs free energy diagram, the first wavefront comes from the solid‐state amorphization reaction between the Ni and a‐Si. The formation of the final Ni silicide causes the second wavefront. The entire reaction is described by a transient heat transfer model. It proposes a key parameter called heat loss rate, which explains the importance of RML thickness and the thermal diffusivity of the substrate. It allows to accurately control the reaction rate, which masters the final silicide phase. Thus, the oxidation of samples downgrades the reliability as the self‐propagation velocity of the two wavefronts dropped to 1.34 and 1.91 m s−1 in samples after 200 h of oxidation.

The Simulated Effect of Adding Solder Layers on Reactive Multilayer Films Used for Joining Processes

In order to introduce new bonding methods in the area of electronic packaging a theoretical analysis was conducted, which should give substantial information about the potential of reactive multilayer systems (rms) to create sufficient local heat for joining processes between silicon chips and ceramic substrates. For this purpose, thermal CFD (computational fluid dynamics) simulations have been carried out to simulate the temperature profile of the bonding zone during and after the reaction of the rms. This thermal analysis considers two different configurations. The first configuration consists of a silicon chip that is bonded to an LTCC-substrate (Low Temperature Co-fired Ceramics) using a bonding layer that contains an rms and a solder preform. The reaction propagation speed of the reactive multilayer was set to a value of 1 m/s, in order to partially melt a solder preform underneath a silicon chip. The second configuration, which consists only of the LTCC-substrate and the rms, was chosen to study the differences between the thermal outputs of the two arrangements. The analysis of the CFD simulations was particularly focused on interpretations of the temperature and liquid fraction contours. The CFD thermal simulation analysis conducted contains a melting/solidification model which can track the molten/solid state of the solder in addition to modelling the influence of latent heat. To provide information for the design of a test-substrate for experimental investigations, the real behaviour of Pt-100 temperature probes on the LTCC-substrate was simulated, in order to monitor an actual bonding in the experiment. All simulations were carried out using the ANSYS Fluent software.

Development of Actuators for Repairing Cracks by Coating W Wires with Reactive Multilayers.

The aim of this research work was to optimize the coating of tungsten wires with reactive multilayer thin films and promote an exothermic self-propagating reaction. The ultimate goal is to use this heat to liquify low melting temperature materials, and thus block crack propagation in metallic materials. Ni/Me (Me = Al, Ti) multilayers were deposited by a DC (direct current) magnetron sputtering onto tungsten wires with diameters of 0.05 and 0.20 mm. The depositions were carried out to obtain films with near equiatomic average chemical composition and a modulation period (bilayer thickness) between 20 and 50 nm. The cross-section of the films was analyzed using electron microscopy before and after electrical ignition. A new substrate holder was developed to improve the quality of the Al/Ni films, allowing a reduction in the defects previously observed. The Ni/Ti thin films showed no discernible defects, regardless of the substrate holder. However, after ignition, the Ni + Ti reaction occurred in a non-self-propagating mode. Passing an electric current through a wire (ϕ = 0.05 mm) coated with an Al/Ni thin film, promoted a flash of light that was associated with the start of a self-propagating reaction. The reaction product was a B2-AlNi intermetallic phase. W wires coated with reactive multilayers may contribute to crack filling, and have potential to be self-healing actuators.