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About this book

This book presents the latest research on the area of nano-energetic materials, their synthesis, fabrication, patterning, application and integration with various MEMS systems and platforms. Keeping in mind the applications for this field in aerospace and defense sectors, the articles in this volume contain contributions by leading researchers in the field, who discuss the current challenges and future perspectives. This volume will be of use to researchers working on various applications of high-energy research.

Table of Contents


Nano-Energetic Materials: The Current Paradigm


Chapter 1. Introduction to Nano-energetic Materials

With the advent of micro- and nano-scale devices, the energy management at molecular level is vital for performance enhancement. The field of nano-energetics focuses on the study of synthesis and fabrication of energetic materials or composites at nano-level. The nano-energetic materials may include almost all materials associated with the generation and storage of energy in all forms, viz., thermal, electrical, chemical, etc. The advantages of nano-scale are many which include characteristics like overall small particle size, large specific surface area, high surface energy and strong surface activity, and all these properties associated with the nano-scale provide a key to obtain an overall high energy turnover from such materials and composites and provide solutions to some very pressing current technology needs. The primary requirement of nano-energetic materials is to obtain an efficient energy release through combustion and other processes at the nano-scale. This is regulated by tuning the proportion of the oxidizer and fuel in combusting materials during the synthesis stage so that the thermite reaction can be stoichiometrically starved or over bred for different energy releases. These materials after synthesis are then interfaced with micro-/nano-scale electromechanical devices so that they can be put to use for concentrated blast release, pulse power generation, thrust generation, energy conversion and various other applications. These nano-structured energetic materials can be utilized as propellants, explosives and pyrotechnics on the basis of their specific spatial arrangements, enactments, and presentation spaces, etc. The various methods that are deployed to fabricate these energetic materials include wet chemical synthesis, DC reactive magnetron sputtering, electrocatalysis, molecular self-assembly. Since these nano-energetic materials and composites have wide scope in micro-/nano-energetic arena of applications, the corresponding book discusses some of the detailed and novel synthesis, fabrication, characterization, tunability, storage and application aspects of these materials.
Shantanu Bhattacharya, Avinash Kumar Agarwal, Vinay K. Patel, T. Raja Gopalan, Aviru Kumar Basu, Anubhuti Saha

Chapter 2. Aluminum-Based Nano-energetic Materials: State of the Art and Future Perspectives

Technological innovations are indeed driven by enhanced abilities to understand and manipulate matter at molecular and atomic scale. Engineering energetic nanocomposites with tailored and tunable combustion characteristics is indispensable for their deployment in both civilian and defense applications. Specifically, a heterogeneous mixture of fuel [aluminum (Al), boron, magnesium, silicon, etc.] and oxidizer [cupric oxide, bismuth trioxide (Bi2O3), ferric oxide, etc.] with both the constituents having nanoscale dimensions constitutes a class of energetic material known as nanothermites. Among various fuels employed in nano-energetic formulations, the number of theoretical and experimental investigations on the utilization of Al outweighs that of any other metallic fuel. Knowledge on the physical and chemical characteristics of the constituents and their impact on combustion performance are fundamental to accelerate the pace of research and development in nano-energetic composites. Efforts to develop comprehensive understanding of the oxidation behavior are discussed in this article. Furthermore, the organization, intimacy, and dimensions of discrete fuels and oxidizers apart from their chemistry largely dictate the combustion kinetics exhibited by nanothermites. For a given nanocomposite, increasing the interfacial contact area between fuel and oxidizer improves its reaction rate by 3–5 orders of magnitude as a result of drastic reduction in mass and heat transport lengths. The bottom-up self-assembly process offers the most realistic solution to enhance the interfacial contacts between nanoscale constituents employing different approaches. This review summarizes the key findings in this area of research and lists the key challenges and opportunities for furthering the application aspects. Enhancement of combustion characteristics of energetic liquids through the utilization of Al and metal oxide nanoparticles as additives is another area of related research that continues to receive increasing attention (Sundaram et al. 2017). Energetic liquids possess unique characteristics such as lower activation temperature, higher pressure, and better volume expansion. Experimental research efforts have demonstrated ample promise for overcoming the inherent problems such as lower energy density and slow burn kinetics associated with energetic liquids. In gist, the central theme of this chapter is devoted to highlight and analyze the recent advancements on aluminum-based nano-energetic materials besides presenting the challenges and opportunities in the domain of nano-energetic materials development.
Rajagopalan Thiruvengadathan

Chapter 3. Nanostructured Energetic Composites: An Emerging Paradigm

Nanotechnology has ushered a remarkable progress in the field of medicine, environment, ceramics, especially considering its applications in the defence sector. This progress has been inspired by the ordered assembly of molecular and nanoscale elements to develop multifunctional smart reactive materials for energetic applications. An important class of these materials is the nano-energetic materials or nanothermites, which are composed of nanometals and nano-oxidizers. A major drawback of classical micron-sized metal particles is that they ignite after a comparatively long delay. These micron-sized metal particles when combined with oxidizer such as metal oxides as in thermite result in metal delays which are usually associated with diffusion of oxidizer and/or fuel through the protective layer of metal oxides. The motive behind nano-energetic materials is to develop a new synthetic procedure, which could limit both the oxidizer and the fuel balance in the thermites. Development of assembly of energetic composite materials (by number of techniques like self-assembly, cold spraying, ball milling, sol–gel, gas-phase processes) is touching new horizons of research. In this chapter, emphasis is laid on the current research focusing on manipulation of individual atoms and molecules to produce organized and systematic structure of nanocomposites for applications in nanothermites. Nanothermites are comparatively a new class of energetic material that consist of metallic fuel and metal oxide-based oxidizer with critical dimensions on the nanoscale. The standard powder-mixing protocol has intrinsic constraints, particularly random distribution of fuel and oxidizer particles and unavoidable fuel pre-oxidation. The present research scenario deals with an alternative approach for nanostructured energetic composites by varied processes. The subsequent sections of this chapter will meticulously describe the strategies adopted for the preparation of such nanostructure assemblies. These hierarchical structures provide desirable performance in combustion, ignition and mechanical characteristics. In the end, some promising applications of nanostructured energetic composites incorporated into various systems ranging from microelectromechanical systems (MEMS) devices to rocket propellants to explosives that permit new functions to be performed are illustrated.
Hema Singh, Shaibal Banerjee

Chapter 4. Nano-energetic Materials for Defense Application

Energetic materials are the reactive materials containing fuels and oxidizers that can liberate chemical energy preserved in their molecular structure. Nano-energetic materials have found to be the potential sources for extremely high heat release rates, tailored burning rate, extraordinary combustion efficiency, and reduced sensitivity. These materials play a vital role in defense applications as a recent advancement in emerging areas such as manufacturing of explosives, solid and liquid propellants, rocket propelling, advanced gun propellant materials. Considering the immense scope of these functional materials, this chapter focuses to cover the fundamental aspect of energetic materials, description of contemporary reported literature on design and synthesis of nano-energetic materials and their significance for microscale applications in the defense sector.
Sudarsana Jena, Ankur Gupta

Chapter 5. Nano-aluminium as Catalyst in Thermal Decomposition of Energetic Materials

Current state of the art propellant and explosive technology relies on the inclusion of nano-metallic fuels such as aluminium nanopowder. Aluminium nanoparticles, a common fuel ingredient in high-energy material developments, can improve the energy density, rate of energy release, ignition, and combustion performance. In this chapter, the catalytic effect of aluminium nanoparticles on thermal decomposition of various high-energy materials is critically reviewed and presented. The combustion behaviour and ballistic performance of these energetic materials are found to be highly modified and influenced by the aluminium nanopowder. The nanoscale aluminium reflects excellent catalytic activity in thermal decomposition of energetic materials with significant reduction in decomposition temperature. The reaction mechanism of aluminium nanoparticles enhancing the decomposition of high-energy materials is detailed.
Amit Joshi, K. K. S. Mer, Shantanu Bhattacharya, Vinay K. Patel

Fabrication of Nano-energetic Materials


Chapter 6. Nano-energetic Materials on a Chip

After integration into an electronic chip, the nano-energetic materials have found a very important role as portable microscale energy systems in many applications such as micro-actuation for micro-fluidics, micro-ignition, micro-propulsion, and onboard micro-power unit. However, there has been an ongoing challenge to fabricate high-reactive and high-energy density nano-energetic materials and integrate it with microelectromechanical system (MEMS) devices. There are various micro-/nanofabrication methodologies to develop and integrate the nano-energetic materials into a chip. This chapter discusses the different approaches and methods of realization of nano-energetic materials on a chip and details about the ignition sensitivity, energy density, and combustion performance. The chapter also particularizes the application of the chip-integrated nano-energetic materials.
Jitendra Kumar Katiyar, Vinay K. Patel

Chapter 7. Nano-/Micro-engineering for Future Li–Ion Batteries

Lithium–ion batteries are the key power sources for this technology based world, mainly in the modern mobile world. These batteries have served as the most prominent energy storage devices in case of smartphones, tablets, laptops, electric vehicles and grid-level storage. They offer many advantage in terms of high energy density, moderately high power density, high voltage, low self-discharge, and moderately long cycle life. There are various nano/micro- engineering techniques involved in fabrication of these devices. This chapter discusses in detail the various aspects of Lithium-ion batteries including storage mechanism to installation of various constituents of the battery.
Prasit Kumar Dutta, Abhinanada Sengupta, Vishwas Goel, P. Preetham, Aakash Ahuja, Sagar Mitra

Chapter 8. Different Approaches to Micro-/Nanofabricate and Pattern Energetic Materials

Nanoscience and nanotechnology have played a tremendous role in stimulating the development of nanoenergetic materials with orders of magnitude increase in the interfacial area and intimacy of contacts of fuel and oxidizer. In the global world, research and development efforts are continuously being made at a very rapid rate to realize high energy density and super-reactive nanoenergetic materials. The reactivity and ignition sensitivity of nanoenergetic materials are significantly enhanced with nanoscaling of reactants (fuel and oxidizers) on the counterpart of microscale reactants. Nano-energetic materials can be easily integrated with the microsystems, which find many promising applications in micro-initiation, micro-ignition, micro-propulsion, micro-power generation, and pressure-mediated gene delivery/transfection. In this chapter, the various fabrication methodologies of nanoenergetic materials have been discussed and detailed with relevance to their energy density, combustion performance (ignition sensitivity, combustion velocity, and pressurization rate), and suitable integration. Further, the formulations and patterning of nanoenergetic materials on silicon substrate are also included as a future potential for micro-electro-mechanical systems energetic devices.
Amit Joshi, K. K. S. Mer, Shantanu Bhattacharya, Vinay K. Patel

Tuning and Characterization of Nano-energetic Materials


Chapter 9. Tuning the Reactivity of Nano-energetic Gas Generators Based on Bismuth and Iodine Oxidizers

There is a growing interest in novel energetic materials called nano-energetic gas generators (NGGs) which are potential alternatives to traditional energetic materials including pyrotechnics, propellants, primers, and solid rocket fuels. NGGs are formulations that utilize metal powders as a fuel and oxides or hydroxides as oxidizers that can rapidly release a large amount of heat and gaseous products to generate shock waves. The heat and pressure discharge, impact sensitivity, long-term stability, and other critical properties depend on the particle size and shape, as well as assembling procedure and intermixing degree between the components. The extremely high energy density and the ability to tune the dynamic properties of the energetic system makes NGGs ideal candidates to dilute or replace traditional energetic materials for emerging applications. In terms of energy density, performance, and controllability of dynamic properties, the energetic materials based on bismuth and iodine compounds are exceptional among the NGGs. The thermodynamic calculations and experimental study confirm that NGGs based on iodine and bismuth compounds mixed with aluminum nanoparticles are the most powerful formulations to date and can be used potentially in microthrusters technology with high thrust-to-weight ratio with controlled combustion and exhaust velocity for space applications. The resulting nano-thermites generated the significant value of pressure discharge up to 14.8 kPa m3/g. They can also be integrated with carbon nanotubes to form laminar composite yarns with high power actuation of up to 4700 W/kg or be used in other emerging applications such as biocidal agents to effectively destroy harmful bacteria in seconds, with 22 mg/m2 minimal content over the infected area.
Mkhitar A. Hobosyan, Karen S. Martirosyan

Nano-energetic Materials: The Emerging Paradigm


Chapter 10. Recent Advancement in the Fabrication of Energy Storage Devices for Miniaturized Electronics

The rapidly increasing need of the energy and the requirement of the current and further generation compact electronic devices have emerged the development of micro-scaled energy storage devices. These energy storage devices should be efficient enough to store the sufficient energy in a limited area. The micro-supercapacitors have reported as the best alternative to power the miniaturized electronic devices. A lot of energy storage materials, fabrication methods, and the electrode design have been explored to achieve the high performance of the micro-scaled energy storage devices. This review focuses on the current progress to fabricate and improve the performance of the micro-supercapacitor devices for their potential application in the miniaturized electronic devices.
Poonam Sundriyal, Megha Sahu, Om Prakash, Shantanu Bhattacharya

11. Solid Energetic Materials-Based Microthrusters for Space Applications

In this global scenario, the current state-of-the-art technologies in energy policy and management systems involve the integration of solid propellants/energetic materials into microelectromechanical system (MEMS) to exploit the onboard thermal, mechanical, and chemical energy for civilian and defense needs. The solid propellants are recognized as attractive onboard energy sources owing to contain high energy density and rapid energy release and high actuation pressure as demanded in micro-propulsion. Microthrusters are used to propel and guide the missiles, shells, and also to orient and propel the satellites and to launch the rockets. This chapter details the technological developments and advancements made in the design, fabrication, and modeling of solid energetic materials (propellants and nano-thermites)-based microthrusters and their characterization in terms of propulsion performance as applied for space applications.
Vinay K. Patel, Jitendra Kumar Katiyar, Shantanu Bhattacharya

12. Nanomaterials for Hydrogen Production Through Photocatalysis

In the last few decades, nanostructured materials have been of great interest worldwide due to their unique characteristics and their sub-driven reactivity. Furthermore, the unlimited applications of such materials in different fields and their associated success had added extra value for their importance. The combination between nanomaterials and photocatalytic processes has been recently given a great attention in different applications. It may enhance the viability of the nanotechnology principles. One of these applications is the usage of nanophotocatalytic materials in hydrogen production via water-splitting reaction. This chapter will cover the main concepts of photocatalysis and its associated terms. The main features of efficient photocatalysts and the ways of measuring such properties are illustrated in this chapter. Also, a brief presentation for the current methods that are utilized in the preparation of these catalysts is provided. An overview of the different types of semiconductors that are employed in the domain of photo-based hydrogen generation via splitting of water is introduced through this chapter too. A new approach in the water-splitting process by introducing noble metals attached magnetic nanoparticle (core/shell structure) as promising photomaterials is also described in this chapter. However, these materials are used in different fields such as bio-medical processes, water treatment, and energy storage. They are expected to be of high significance in field of catalysis, since they can be easily separated and recovered, due to their magnetic character, for reuse in further reactions. Implementation of a suitable magnetic force can enhance the hydrogen productivity during the water-splitting process. These materials are possessing magnetic properties which could reveal a new approach to their photocatalytic activity via quenching the radiation scattering.
Ahmed M. A. El Naggar, Mohamed S. A. Darwish, Asmaa S. Morshedy

Chapter 13. Interface Mechanical Properties in Energetic Materials Using Nanoscale Impact Experiment and Nanomechanical Raman Spectroscopy

Energetic materials are sensitive to mechanical shock and defects caused by a high-velocity impact may result in unwanted detonation due to hot-spot formation. In order to understand the underlying mechanism, characterization of high strain-rate mechanical properties needs to be studied. One of the key factors that can contribute to this type of defect is the failure initiated at the interfaces such as those between Hydroxyl-terminated polybutadiene (HTPB) and Cyclo-tetra-methylene-tetra-nitramine (HMX) (or HTPB and Ammonium Perchlorate (AP)). In this work, interface mechanical properties of HTPB-HMX and HTPB-AP interfaces are characterized using nanoscale dynamic impact experiments at strain rates up to 100 s−1. The binding agent was added to the mixture in order to analyze the effect of chemical composition on the interfacial mechanical properties. For HTPB-AP sample, Tepanol is used as the binding agent and for HTPB-HMX sample, Dantocol was used as the binding agent. The impact response is determined in the bulk HTPB, HMX, and AP as well as at the HTPB-HMX and HTPB-AP interfaces. A strain-rate-dependent viscoplastic power law-based constitutive model was obtained by fitting the experimental stress–strain–strain-rate data. The effect of binding agent on interface level failure properties was studied using an in situ nanomechanical Raman spectroscopy (NMRS) setup.
Chandra Prakash, Ayotomi Olokun, I. Emre Gunduz, Vikas Tomar
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