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    Nanomaterials in Rocket Propulsion Systems
    Nanomaterials in Rocket Propulsion Systems
    Nanomaterials in Rocket Propulsion Systems
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    Nanomaterials in Rocket Propulsion Systems

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    Nanomaterials in Rocket Propulsion Systems covers the fundamentals of nanomaterials and examines a wide range of innovative applications, presenting the current state-of-the-art in the field. Opening with a chapter on nano-sized energetic materials, the book examines metal nanoparticles-based fuels, ballistic modifiers, stabilizers and catalysts as the components of rocket propellants. Hydrogen storage materials for rocket propulsion based on nanotubes are then discussed, as are nano-porous materials and metal organic frameworks, nano-gelled propellants, nano-composite ablators and ceramic nano-composites. Other applications examined include high thermal conductivity metallic nano-composite nozzle liners, nano-emitters for Coulomb propulsion of space-crafts, and highly thermostable nano-ceramics for rocket motors.

    The book finishes with coverage of combustion of nano-sized rocket fuels, nano-particles and their combustion in micro- and nano-electromechanical systems (MEMS/NEMS), plasma propulsion and nano-scale physics. Users will find this to be a valuable resource for academic and government institutions, professionals, new researchers and graduate students working in the application of nanomaterials in the aerospace industry.

    • Provides a detailed overview of different types of nanomaterials used in rocket propulsion, highlighting different situations in which different materials are used
    • Demonstrates the use of new nanomaterial concepts, allowing for an increase in payload capacity or a decrease in launch mass
    • Explores a range of applications using metal nanopowders, presenting a panorama on cutting-edge, technological developments
    LanguageEnglish
    PublisherElsevier Science
    Release dateOct 16, 2018
    ISBN9780128139097
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      Nanomaterials in Rocket Propulsion Systems - Qi-Long Yan

      Nanomaterials in Rocket Propulsion Systems

      Editors

      Qi-Long Yan

      Guo-Qiang He

      Pei-Jin Liu

      Michael Gozin

      Table of Contents

      Cover image

      Title page

      Copyright

      Dedication

      Contributors

      Preface

      Part 1. Nanomaterials in Rocket Fuels

      Chapter 1. The Prospects of Using Nanoenergetic Materials in Solid Rocket Propulsion

      1. Introduction

      2. Nanometals in Solid Propellants

      3. Nano-Oxidizers

      4. Mechanisms of Nanothermite Reaction

      5. Nano-Explosives

      6. Experimental Methods for Characterization of Nanoenergetic Systems

      7. Concluding Remarks

      Chapter 2. Review on Nanoexplosive Materials

      1. Introduction

      2. Why Nanoexplosives

      3. Preparation and Characterization

      4. Properties

      5. Challenges Involved

      6. Conclusion and Outlook

      Chapter 3. Insensitive Energetic Materials Containing Two-Dimensional Nanostructures as Building Blocks

      1. Introduction

      2. Graphene-Based Energetic Nanomaterials

      3. Carbon-Nitrogen-Based 2D Energetic Structures

      4. Summary

      Chapter 4. Preparation, Characterization, and Application of Superthermites in Solid Propellant

      1. Introduction

      2. Experiment Section

      3. The Thermal Behaviors and Decomposition Mechanisms of the Precursors for Al/CuO Superthermite

      4. Compatibility of Superthermite With the Components of DB Propellants [26]

      5. The Effects of Superthermites on the Combustion Properties of DB Propellants

      6. Conclusion

      Chapter 5. Aluminum Powders for Energetics: Properties and Oxidation Behavior

      1. Introduction

      2. Al Nanopowder

      3. Oxidation of Al Powders

      4. Combustion of Al Powders in Air

      5. Oxidation of Al Powders in Water

      6. Al Powder Combustion in Propellants

      7. Conclusion

      Part 2. Nano-Engineered Propellants and Propulsion

      Chapter 6. Nanoenergetic Ingredients to Augment Solid Rocket Propulsion

      1. Background

      2. Motivations and Objectives

      3. Historical Excursus in Solid Rocket Propulsion

      4. Introduction to Nanometals

      5. Studies on Nanoingredients for Solid Rocket Propulsion

      6. Basic Flame Structure Modified by Aluminum Powder

      7. Augmented Steady Ballistic Properties

      8. Delivered Specific Impulse

      9. Concluding Remarks

      Chapter 7. Performance of Composite Solid Propellant Containing Nanosized Metal Particles

      1. Introduction

      2. Experimental

      3. Results and Discussion

      4. Conclusions

      Chapter 8. Effect of Ammonium Perchlorate Particle Size on Flow, Ballistic, and Mechanical Properties of Composite Propellant

      1. Introduction

      2. Theoretical Background

      3. Experimental Procedures

      4. Results and Discussion

      5. Conclusion

      Chapter 9. New Developments in Composite Propellants Catalysis: From Nanoparticles to Metallo-Polyurethanes

      1. Introduction

      2. Nano-TMOs as BR Catalysts

      3. Metallo-PUs as BR Catalysts

      4. Conclusion

      Chapter 10. Chemical Propulsion of Microthrusters

      1. Introduction

      2. Solid Propellants for Microhrusters

      3. Conclusion

      Chapter 11. Integrated Micropropulsion Systems With Nanoenergetic Propellants

      1. Introduction

      2. Solid Propellants

      3. Nanoenergetic Materials

      4. Nanoenergetic Gas Generator Formulations for Microthrusters

      5. Design and 3D Printing of Microthrusters and Microthruster Arrays

      6. Dispensing and Encapsulation of Nanoenergetic Materials

      7. Microthruster Testing and Thrust Evaluation

      8. Sensing and Communication Technologies in Aerial Vehicles With Microthrusters

      9. Conclusions

      Part 3. Nanomaterials for Rocket Motors Hardware

      Chapter 12. Polymer Nanocomposite Ablative Technologies for Solid Rocket Motors

      1. Introduction

      2. Solid Rocket Motor Nozzle and Insulation Materials

      3. Advanced Polymer Nanocomposite Ablatives

      4. New Sensing Technology

      5. Technologies Needed to Advance Polymer Nanocomposite Ablative Research

      6. Overall Summary and Conclusion

      Chapter 13. Nanotube/Nanowire-Toughened Carbon/Carbon Composites and Their Coatings

      1. Introduction

      2. Nanoparticle-Toughened Coatings on C/C Composites

      3. Carbon Nanotube-Toughened Coatings on C/C Composites

      4. SiC Nanowire-Toughened Coatings on C/C Composites

      5. SiC Nanowire-Toughened C/C–UHTC Composites

      6. HfC Nanowire-Toughened Coatings on C/C Composites

      7. Summary

      Chapter 14. An Introduction to Ablative Materials and High-Temperature Testing Protocols

      1. An Introduction to Thermal Protection System Materials

      2. Polymeric Ablatives

      3. Advanced Testing Techniques for TPS Materials

      Author Index

      Subject Index

      Copyright

      Elsevier

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      Notices

      Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

      Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

      To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

      Library of Congress Cataloging-in-Publication Data

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      ISBN: 978-0-12-813908-0

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      Dedication

      By making calligraphy above, Prof. Guo-Qiang He, as one of the editors of this book and vice president of the Northwestern Polytechnical University (NPU), would like to commemorate and celebrate the 80th anniversary of the foundation of NPU, meantime the 60th anniversary of the School of Astronautics in this university.

      Contributors

      Ting An,     Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an, China

      A.N. Arnautov

      National University of Science and Technology MISiS, Moscow, Russia

      RUSAL Co., Moscow, Russia

      Jauhari Ashish,     High Energy Materials Laboratory (HEMRL), Ministry of Defence, Pashan, Pune, India

      Kandasubramanian Balasubramanian,     Department of Materials Engineering, Defence Institute of Advanced Technology (DU), Ministry of Defense, Girinagar, Pune, India

      Ji Dai,     School of Chemical Engineering, Nanjing University of Sciecne and Technology, Nanjing, China

      Luigi T. De Luca

      Politecnico di Milano, Milan, Italy

      Nanjing University of Science and Technology, Nanjing, China

      Space Propulsion Laboratory (SPLab), Politecnico di Milano, Milan, Italy

      XueZhong Fan,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      Qian-Gang Fu,     National Key Laboratory for Thermostructure Composite Materials, Northwestern Polytechnical University, Xi'an, China

      XiaoLong Fu,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      Bing Gao,     Institute of Chemical Materials of China Academy of Engineering Physics, Mianyang, Sichuan, China

      Michael Gozin,     School of Chemistry, Tel Aviv University, Tel Aviv, Israel

      A.A. Gromov

      National University of Science and Technology MISiS, Moscow, Russia

      Tomsk Polytechnic University, Tomsk, Russia

      Guo-Qiang He,     Science and Technology on Combustion, Thermo-structure, and Internal Flow Laboratory, Northwestern Polytechnical University, Xian, China

      Mkhitar Hobosyan,     Department of Physics and Astronomy, University of Texas at Rio Grande Valley, Brownsville, TX, United States

      Carlos Hortelano,     Instituto Nacional de Técnica Aeroespacial Esteban Terradas, INTA, Torrejón de Ardoz, Spain

      Joseph H. Koo,     The University of Texas at Austin, Department of Mechanical Engineering, Austin, TX, United States

      Jon Langston,     The University of Texas at Austin, Department of Mechanical Engineering, Austin, TX, United States

      K.B. Larionov,     Tomsk Polytechnic University, Tomsk, Russia

      Huan Li,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      JunQiang Li,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      Pei-Jin Liu,     Science and Technology on Combustion, Thermo-structure, and Internal Flow Laboratory, Northwestern Polytechnical University, Xian, China

      José Luis de la Fuente,     Instituto Nacional de Técnica Aeroespacial Esteban Terradas, INTA, Torrejón de Ardoz, Spain

      Sergey E. Lyshevski,     Department of Electrical and Microelectronic Engineering, Rochester Institute of Technology, Rochester, NY, United States

      Karen S. Martirosyan,     Department of Physics and Astronomy, University of Texas at Rio Grande Valley, Brownsville, TX, United States

      A.Yu. Nalivaiko,     National University of Science and Technology MISiS, Moscow, Russia

      Maurizio Natali,     University of Perugia, Civil and Environmental Engineering Department, Terni, Italy

      WeiQiang Pang,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      Zhiqiang Qiao,     Institute of Chemical Materials of China Academy of Engineering Physics, Mianyang, Sichuan, China

      Wen-Gang Qu,     Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an, China

      Marco Rallini,     University of Perugia, Civil and Environmental Engineering Department, Terni, Italy

      Chengbo Ru,     School of Chemical Engineering, Nanjing University of Sciecne and Technology, Nanjing, China

      A.V. Sergienko,     Tomsk Polytechnic University, Tomsk, Russia

      Ruiqi Shen,     School of Chemical Engineering, Nanjing University of Sciecne and Technology, Nanjing, China

      Qiang Song,     National Key Laboratory for Thermostructure Composite Materials, Northwestern Polytechnical University, Xi'an, China

      Gharde Swaroop,     Department of Materials Engineering, Defence Institute of Advanced Technology (DU), Ministry of Defense, Girinagar, Pune, India

      V.P. Tarasov,     National University of Science and Technology MISiS, Moscow, Russia

      Luigi Torre,     University of Perugia, Civil and Environmental Engineering Department, Terni, Italy

      Chengling Wang,     School of Chemical Engineering, Nanjing University of Sciecne and Technology, Nanjing, China

      Ke Wang,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      HuiXiang Xu,     Xi'an Modern Chemistry Research Institute, Xi'an, People's Republic of China

      Qi-Long Yan

      Science and Technology on Combustion, Thermo-structure, and Internal Flow Laboratory, Northwestern Polytechnical University, Xian, China

      Science and Technology on Combustion and Explosion Laboratory, Xi’an Modern Chemistry Research Institute, Xi’an, China

      Guangcheng Yang,     Institute of Chemical Materials of China Academy of Engineering Physics, Mianyang, Sichuan, China

      Yan-Jing Yang,     Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an, China

      Yinghua Ye,     School of Chemical Engineering, Nanjing University of Sciecne and Technology, Nanjing, China

      Vladimir E. Zarko

      Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia

      Tomsk State University, Tomsk, Russia

      Feng-qi Zhao,     Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an, China

      Lei Zhuang,     National Key Laboratory for Thermostructure Composite Materials, Northwestern Polytechnical University, Xi'an, China

      S.V. Zmanovsky,     RUSAL Co., Moscow, Russia

      Preface

      Nanomaterials and nanotechnology have made a significant contribution to modern industry and economy. In particular, state-of-the-art rocket propulsion systems have greatly benefited from nanotechnology development in recent years, especially in terms of nanomaterials for rocket fuels and fabrication of microthrusters. On the occasion of the 80th anniversary of the foundation of NPU, and the 60th anniversary celebration of its School of Astronautics, this book is organized as a milestone of advanced research in solid rocket propulsion technologies. The book presents compiled results of the most recent development in applications of nanomaterials and nanotechnology in rocket propulsion systems. This relatively new and highly active research field has already led to several breakthroughs in the development of advanced propellants, microenergetic devices, and rocket motors. In the case of nanosized ingredients for solid propellants, a common advantage is their great reactivity, resulting in extremely fast and highly efficient burning. The most advanced nanomaterials for propulsion systems include metal-based composites, crystalline nanoenergetic compounds, nanosized combustion catalysts, and ablative nanomaterials, as well as nano-coating materials for rocket motor cases, and nozzle coatings, nanostructured ingredients, and components for microthrusters, which make use of energetic nanocomposites and integrate them into microchips.

      This book with 14 chapters summarizes the most recent achievements of the leading research groups working in the field of rocket propulsion systems in China, the United States, Russia, India, Israel, Italy, and Spain. Chapter 1 presents an overview of nanoenergetic materials and recent achievements in studying their reaction mechanisms. This knowledge allows creation of molecularly manipulated energetic substances and formulations having tailored chemical and physical properties. Chapter 2 provides an overview of the main developments in three types of nanosized explosives that can be used as ingredients of propellants, in terms of their preparation, characterization, and properties. Attention is paid to the relationships between particle size at the nanoscale and corresponding performance on nanosized effects. Chapter 3, in particular, focuses on novel two-dimensional nanoenergetic materials (2D EMs) as promising components of propellants. The preparation, characteristics, and performance of various types of 2D EMs, containing pristine graphene, chemically functionalized graphene, and other nongraphene-based materials, are described. Chapters 4 and 5 describe nanometals and corresponding nanocomposites. As a typical example, the features of aluminum nanopowder are discussed along with its reaction kinetics and oxidation behavior in different oxidation media, from reaction with strong oxidizers, in the case of rocket propulsion, to reaction with relatively weak oxidizers such as air (and even with water). The preparation and characterization of Al-based superthermites and their applications in propellants and microthrusters are systematically summarized in these chapters. The introduction of superthermites in propellants would enhance burning rates and decrease pressure exponents, indicating that these nanomaterials are of high catalytic activity in propellant combustion.

      In the case of nanoengineered propellants, in spite of the intense worldwide research effort, only laboratory-level applications have been mostly reported. Chapters 6 and 7 present a number of practical reasons preventing the scaling-up of nanoengineered propellants and their applications at an industrial level, which include inert natural coating of energetic particles, nonuniform dispersion, excessive viscosity of slurry propellants, possible limitations in mechanical properties, as well as safety issues. These two chapters also describe the main features in terms of performance of solid rocket propellants loaded with nanosized energetic ingredients (NEI), emphasizing the unique properties and operating conditions made possible by the addition of NEI. Several industrial- and research-type composite solid propellants, containing different nanosized metal particles, such as Al, Zr, and Ti, with similar nominal compositions, were prepared and experimentally analyzed. Nanosized additives can affect the combustion behavior and increase the burning rate of propellants.

      Chapter 8 is focused on composite propellants that are based on hydroxyl-terminated polybutadiene and nanosized ammonium perchlorate (AP), which play a vital role in tailoring the burning rate of these propellants. AP is ground into different particle sizes for use in such propellant formulations to achieve different burn rates and higher solid loadings, because AP with submicron sizes has a large surface area and excessive surface energy. As an alternative methodology for tuning the burning behavior, nanocatalysts could be added to the AP-based propellants. Chapter 9 describes the effects on the performance of AP-based composite propellants by employing nanopowders of transition metal oxides, such as Fe2O3, CuO, and TiO2. The nanoengineered propellants produce highly stable burning rates over a broad pressure range. It is further indicated that the incorporation of both metallic oxide nanoparticles and polymeric organometallic catalysts, based on ferrocene, in the formulations of these energetic materialss could improve their ballistic and combustion properties.

      As a further supplement, Chapters 10 and 11 present the latest developments in the design of integrated microthrusters and thruster arrays, using nanoenergetic composites as propellants. Nanostructured energetic composites based on bismuth hydroxide and aluminum nanoparticles generate adequate thrust, heat, and gas flow. Experimental validation and characterization of three-dimensional printed microthrusters and thruster arrays are described. In these chapters, developments designed to guarantee robustness, stability, and thermal control of advanced nanoenergetic materials for aerial systems, as well as advanced sensing, are also outlined. In addition to nanoengineered propellants, nanomaterials and technology that are used in rocket motors, especially for ablation purposes, are described.

      Chapters 12–14 deal with the use of thermal protection materials for two key components of solid rocket motors (SRMs): the exhaust nozzle and internal motor insulation. Three important research areas are discussed in these chapters: (1) advanced polymer nanocomposite (PNC) ablatives: PNCs for SRM nozzle and PNCs for SRM internal insulation, (2) new sensing technologies: in situ ablation recession and thermal sensing, and char strength sensing, and (3) technologies needed to advance PNC ablative research: thermophysical properties characterization and ablation modeling. In particular, Chapter 13 describes one-dimensional nanomaterials, such as carbon nanotubes and carbide ceramic nanowires, as the ideal reinforcement additives for development of advanced ultrahigh temperature structural composites that could be used in rocket propulsion systems. Chapter 14 summarizes the relevant generalities on ablative nanomaterials and the related testing techniques. Such techniques include high temperature thermal analyses, the oxy-acetylene torch tests, and the simulated measurements of the solid rocket motor ablating processes. The latter two ensure better understanding of the responses of the ablative materials under real working conditions.

      The organization of this book was initiated in early 2017, and the outline was first reviewed by four experts, who provided invaluable suggestions and should be greatly appreciated. To improve the quality of this book, many other experts were involved as external reviewers of the chapters in addition to us as the editors. Those experts include Prof. Dr. Djalal Trache from the Ecole Militaire Polytechnique University in Algeria, Prof. Dr. Amrousse Rachid from the University of Chouaib Doukkali in Morocco, Prof. Dr. Charles Dubois from the École Polytechnique de Montréal in Canada, Prof. Oleg G. Glotov from the Russian Academy of Sciences, Prof. Nikita V. Muravyev from the Semenov Institute of Chemical Physics in Russia, Prof. Dr. Kangzhen Xu from the Northwestern University in China, Prof. Xuehai Ju from the Nanjing University of Science and Technology in China, Prof. Yanjing Yang from the Xi'an Modern Chemistry Research Institute in China, and Prof. Songqi Hu and Prof. Maolin Chen from the Northwestern Polytechnical University in China. Finally, we especially thank the managing editors of this book from Elsevier and VBRI Press, Dr. Serena Castelnovo, Dr. George Mishra, Dr. Kent Charlotte, and Dr. Holt Simon, for their patience and kind support. Without their work, this book would not be organized and published. The editors sincerely hope that the research efforts described in this book will continue to exhibit fast growth and lead to maturation of advanced technologies, which will improve the quality of rocket propulsion systems for better defense and space exploration.

      The Book Editors

      Q.-L. Yan, G.-Q. He, P.-J. Liu, and M. Gozin

      2018.1.8 in Xi'an, China

      Part 1

      Nanomaterials in Rocket Fuels

      Outline

      Chapter 1. The Prospects of Using Nanoenergetic Materials in Solid Rocket Propulsion

      Chapter 2. Review on Nanoexplosive Materials

      Chapter 3. Insensitive Energetic Materials Containing Two-Dimensional Nanostructures as Building Blocks

      Chapter 4. Preparation, Characterization, and Application of Superthermites in Solid Propellant

      Chapter 5. Aluminum Powders for Energetics: Properties and Oxidation Behavior

      Chapter 1

      The Prospects of Using Nanoenergetic Materials in Solid Rocket Propulsion

      Vladimir E. Zarko¹,²     ¹Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia     ²Tomsk State University, Tomsk, Russia

      Abstract

      Nanoenergetic materials became available during last three decades and offer a promise of much higher energy densities and faster rate of energy release than conventional explosives and solid propellants. The energy densities in nanoenergetic devices can reach 50  MJ/kg. Extremely fast burning rates exceeding 3 km/s can be realized in the combustion of porous silicon nanoenergetic composites. The chapter presents a brief review of novel achievements in studying the reaction mechanisms of nanoenergetic materials. This knowledge would allow the creation of molecularly manipulated energetic substances and formulations with well-tailored chemical and physical properties.

      Keywords

      Bottom-up approach; Combustion; Explosive; Nanoenergetic material; Nanostructured; Propellant; Propulsion; Solid rocket

      Chapter Outline

      1. Introduction

      2. Nanometals in Solid Propellants

      3. Nano-Oxidizers

      4. Mechanisms of Nanothermite Reaction

      5. Nano-Explosives

      6. Experimental Methods for Characterization of Nanoenergetic Systems

      7. Concluding Remarks

      Acknowledgments

      References

      1. Introduction

      Nanostructured energetic materials are those that are characterized by the nanoscale in at least one dimension. Thus these might not only be round-shaped particles but also different kinds of foils, flakes, etc. The nano concept, which includes nanoscience and nanotechnology, was introduced in the middle of the 20th century. In 1959 the Noble Prize winner R. Feynman stated in his lecture in CalTech, Pasadena: But I am not afraid to consider the final question as to whether, ultimately—in the great future—we can arrange the atoms the way we want; the very atoms, all the way down! In the year 2000, when they (researchers) look back at this age, they will wonder why it was not until the year 1960 that anybody began seriously to move in this direction [1].

      In fact, the definition of nanomaterials is somewhat arbitrary and can be based on different criteria. First of all it involves the scaling measure and usually corresponds to submicron sizes. In various fields of science and technology, different subdivisions of length are used to define coarse and fine particles. Formally, 100  nm is accepted as a boundary between ultrafine and nanosized particles. However, one may define this boundary as corresponding to sharply changing the physical properties, e.g., melting temperature. Such a boundary depends on the nature of the substance, and for Al it is about 15  nm, for Au 50  nm, etc. It is a consequence of the classical Gibbs–Thomson equation where the surface energy term shifts the balance of the free energies of the crystalline and molten state that results in melting temperature depression.

      It has to be mentioned that nanostructured materials have been known and used in human practice for many centuries (the Lycurgus Cup, British Museum; church windows; etc.), and M. Faraday was probably the first scientist who studied the properties of matter in nanoform as far back as 1847 [2]. In addition, many scientists who were working in biology had to deal with nano objects many years before the Feynman lecture. However, attention to energetic materials in nanoform has attracted attention only in the latter part of the 20th century.

      The definition of nanotechnology generally includes intentionally made nanomaterials. It has been underlined [3] that like any new innovation, nanotechnology develops by passing through typical periods: prebuzz, buzz, rave reviews, saturations, overhyped, blacklash, and blacklash-to-the-blacklash. This can be drawn in the form of a sine-shaped plot with the first maximum at saturation point and the minimum at blacklash point. Various technologies have their particular behavior, and the situation with nanoenergetic materials has been ingeniously described by M. Zachariah [4]. He stressed that the interest in such materials lies in fundamental thermodynamic limitations that one gets by using traditional CHNO systems. It is a common understanding that typical CHNO-based chemical systems are near the limit of stored chemical energy. Potential benefits of using nanoenergetic materials are their high volumetric energy density and the capability to produce environmentally benign products, as well as their controlled rate of energy release and reduced sensitivity. This made reactive nanocomposites an attractive material for wide applications, including environmentally clean primers, detonators, improved rocket propellants and explosives, thermal batteries, and many others.

      In the past, it was a great expectation that nanoparticles may contain excessive energy associated with high compressive forces in small size particles. Later on, it was revealed theoretically and experimentally that there are no noticeable advantages for nanoscale objects with sizes corresponding to practical applications (30–100  nm). At the same time the close proximity (a few angstroms) between fuel and oxidizer components in energetic material must result in strong acceleration of the chemical reaction rate. These expectations have been justified but only partly because the experimentally observed effects turned out to be less than expected. As stated in [4], we still do not have a good conceptual grasp of many of the initiation and propagation processes in such systems, which are significantly more heterogeneous than the molecular counterparts. Therefore it is necessary to pay special attention to the fundamentals of the processes of nanoparticle reactions to get an answer to the question: how can we make a good (optimal) nanoenergetic composite?

      Along with detailed research on Al-based reactive nanomaterials, essential progress has also been made in creating improved quality high-explosive materials. It was established in theoretical and experimental studies that the explosives' sensitivity to external stimuli decreases with decreasing crystal size. This gave the impetus to work on the synthesis of nanocrystals of different explosives (cyclotrimethylenetrinitramine, RDX; cyclotetramethylenetetranitramine, HMX; hexanitrohexaazaisowurtzitane [HNIW], CL-20; triaminotrinitrobenzene, TATB) by using evaporation-assisted, sol–gel, and other techniques. In addition, different applications of nanoenergetic materials in the form of nanocatalysts, carbon nanotubes, and impregnated porous silicon have been developed in recent times.

      This chapter presents a brief review of novel achievements in the field of nanoenergetic materials applied to solid rocket propulsion systems, and the author understands well that the review might not be exhaustive because this field of science and technology is developing fast and the volume of literature increases vastly. A lot of useful information can be found in the reviews [5–8] and a recent book [9]. Hopefully, the reader will find useful information in the recommended literature and in this chapter.

      2. Nanometals in Solid Propellants

      The replacement of coarse metal fuel powders in solid propellants with nanometal powders became a common tendency in the past. It was expected that propellants with unique properties would be obtained and it was believed that the emergence of nanostructured rocket propellant would open up new directions for the development of this highly concentrated and efficient source of energy. The idea behind the replacement of micron-sized Al in the propellant formulation stated that along with enhancement of the burning rate, its dependency on pressure would decrease. The pioneering results obtained in the 1960s in the Institute of Chemical Physics (Moscow) demonstrated that the burning rate of model propellants based on ammonium perchlorate (AP) and bitumen binder with total replacement of 13%–31% of 15  μm Al with nano-Al (Gen-Miller type, 90  nm [10,11]) was increased by about 50%, but at the same time the pressure exponent was also increased by about 10% [12]. It has to be mentioned that this information was obtained much earlier (by about 20  years) than similar information in the West.

      Later on, numerous attempts to realize the lessening of the pressure exponent in experiments with partially replaced micron-sized Al in solid propellants had failed [13–15]. The experiments have shown that the heat release in the condensed phase becomes enhanced in the presence of nano-Al particles, which results in increased burning rate. However, it was also revealed that when replacing micron-sized Al with nano-Al, the total energy content in solid propellant decreases due to excessive volumetric content of Al2O3 in the nanoparticles (the smaller the particle size, the higher the oxide fraction). This leads to a decrease in the performance efficiency of solid propellant. Particularly, in the case of model propellant formulation (70% AP and 15% energetic binder) containing 15% Al a replacement of ordinary 15 micron-sized Al (99.5% of active metal) with 80  nm Al (82.3% of active metal) leads to a decrease in ideal specific impulse values from Isp(15% Al)  =  266.6  s to Isp(12.3% Al)  =  260.6  s (2.25%). These values are estimated for a chamber pressure of 40  atm and a nozzle exit pressure of 1  atm without taking into account the effect of two-phase losses of specific impulse. Similar conclusions are made in Ref. [16]. It is stated that for typical containing AP, Al, and HTPB (hydroxy terminated polybutadiene) propellant (68/18/14 by mass) the evaluating effect of metal content depletion on gravimetric-specific impulse comprises about a 3% loss at 15% reduction in metal content.

      In the beginning of exploring electro-exploded nano-Al particles (ALEX) some researchers assumed the presence of additional enthalpy of formation stored in submicron metal particles due to nonequilibrium processes of electrical wire explosion and metal condensation that may contribute to the total energy content of the propellant. The idea of the existence of energy excess (up to 400  cal/g) in Al nanoparticles was proposed in Ref. [17]. Some years later this effect was studied in detail [18]. It was revealed in differential thermal analysis experiments that, for Al (50–100  nm) nanoparticles produced by the wire electro-explosion method and aged for 0.5–1.5  years, no effect of stored energy existed. The recorded weak exothermic peak at 580°C is associated with oxidation of the particles due to the presence of small amounts of oxygen impurities in the purge gas (argon or helium), and also with the possible effect of adsorbed air. It should be noted that the effect of stored energy has to be manifested in the value of delivered specific impulse of the solid propellant. However, an increased amount of oxide in nanosized Al particles can reduce and disguise this effect. Therefore the correct impulse detection requires detailed and specialized measurements that can be performed in the future.

      Numerous efforts have been directed in recent years toward the development of methods to synthesize metal particles without a passivating oxide layer. An advanced method for protecting active metal against oxidation in air might be the use of organic self-assembling monolayers, which are densely packing organic films organized on the surface of a certain material via chemisorption of a molecular amphiphile [19]. It was expected that in the case of one organic molecule-thick layer the contamination of metal particles would be extremely small. However, in practice the content of active aluminum in the particles of 80–100  nm size passivated by perfluoroalkyl carboxylic acid (C13F27COOH) became equal to only 23%–25% [20,21].

      Another method of passivating nanometal particles has been suggested in [11,22]. The original nano-Al particles of 50  nm size were produced by Gen-Miller flow-levitation installation via metal evaporation and following condensation in a gas mixture of hexamethyldisilazane vapors with argon. This resulted in the formation of a trimethylsiloxane coating on Al nanoparticles with small changes in particle size from 48 to 54  nm. Surprisingly, the content of active Al was found to change only slightly from 72.5% for oxide coated to 74.5% for polymer coated. This small difference in active Al content remained in both types of particles after 60  days' storage (64.4% for oxide coated and 66.6% for polymer coated). This information demonstrates great technical difficulties in passivating the surface of metal particles without loss of the content of active metal. In fact, the problem remains unsolved all over the world.

      A specific drawback of using nanometal particles is that due to their large specific surface, the viscosity of propellant slurry at the particles content exceeding 10  wt% becomes too high that prevents the application of casting technology in the production of solid propellants.

      With traditional heterogeneous materials, the specific surface Ssp (total surface that 1  g of material contains) is within the 0.05–2  m²/g range. With pure surface metal nanopowders, Ssp could vary in the range of 7–40  m²/g or even higher. The presence of oxide coating could raise this value up to 50–70  m²/g. Spheroidizing of the particles reduces the Ssp of powders and, reversely, in particles with an irregular shape, Ssp could reach very high values. The enlarged Ssp causes an increase in the influence of surface effects (adhesion, friction, etc.). The study of rheological characteristics of the HTPB-based suspensions filled with aluminum shows the following relationship for relative viscosity as a function of solid additives volume concentration Cv [23]:

      This equation is valid for the volume concentration of metal nanoparticles up to 50  vol%.

      3. Nano-Oxidizers

      Much effort has been made throughout the world to desensitize explosives against accidental initiation. For several years, nanostructuring of explosives was a promising field of research aiming for this goal. The continuous preparation process of nano-β-HMX and a promising approach toward the desensitization of nanoenergetic materials is described in Ref. [24]. By means of the spray flash-evaporation technique, nano-explosives and nanocomposites with reproducible properties can be prepared in a single processing step. By increasing the thermal effusivity of an energetic nanomaterial the heat created by hot spots can be more rapidly dissipated, reducing the risk of an unwanted reaction. Using the spray flash-evaporation process, multiple grams of nano- and submicrometer-sized HMX were prepared, having a median particle size of around 116  nm [24]. The formation of the β-polymorph was confirmed by its Raman spectra. The addition of a small amount of Clariant Licowax BJ to the starting solution enables the formation of a slightly less impact-sensitive HMX/Licowax composite. It is assumed that the increase in thermal diffusivity through the addition of thermal conducting materials has a beneficial effect on the impact sensitivity of the explosives.

      In reference [25], nanoparticles of RDX were prepared by a simple reprecipitation method using acetone as solvent and water as antisolvent. The effect of changing experimental parameters such as ratio of solvent to antisolvent, temperature of antisolvent during injection, concentration of solution on particle size and morphology of RDX was systematically studied. The size of the particles was characterized using dynamic light scattering and field emission scanning electron microscopy (FESEM). The mean particle size of the RDX nanoparticles according to FESEM analysis was in the range from 40 to 230  nm under different conditions of preparation. The UV/Vis absorption maximum of nano-RDX was found to be blue shifted when compared to the absorption maximum for bulk RDX. Powder X-ray diffraction results showed that RDX nanoparticles precipitated in the stable α-crystalline form. Fourier transform infrared spectroscopy was used to characterize the chemical nature of the nano-RDX. Thermal characterization of the RDX nanoparticles was done using simultaneous thermogravimetric analysis coupled with differential scanning calorimetry.

      Another approach to obtain nanocrystalline grades of RDX was suggested in Ref. [26]. The nanoparticles of RDX with two characteristic sizes ca. 200 and 500  nm were produced by the rapid expansion of supercritical solutions process. The initiation properties were evaluated for uncoated and wax-coated specimens. Impact and shock sensitivity tests revealed that the nanocrystalline grades were generally less sensitive in a direct comparison with coarser grades of RDX. An unexpected minimum in sensitivity with crystal size was observed in both impact and shock sensitivity test data. The minima occurred at a mean crystal size in the vicinity of 500  nm. For specimens made with the 500  nm and coarser grades of RDX, shock sensitivity increased with the crystal size, which is consistent with the expectation that at lower crystal sizes the correspondingly smaller voids will increase the threshold for critical hot spot formation. The markedly higher sensitivity exhibited by the 200  nm RDX compared to the 500  nm RDX reveals that below a certain crystal size the sensitization effect occurs to both shock and impact stimuli. A further study aimed at accurately determining the mean crystal size, which corresponds to the observed sensitivity minima, may become a key issue in attaining the optimal form of RDX.

      A rather simple evaporation method to obtain nanoparticles of energetic materials was reported in Ref. [27]. The cold-wall vacuum co-deposition process has been successfully used to obtain ammonium nitrate (AN), RDX nanopowders and AN/RDX, Al/polymer nanocomposites. By varying the experimental conditions, nanocomposites with different Al concentrations have been synthesized. Transmission electron microscopy analyses of nanocomposites with Al contents above the percolation threshold show spherical pure metal nanoparticles with a mean diameter of 10  nm, while below the percolation threshold the composite contains agglomerates of rhombohedral Al2O3 (corundum) with an average size of 55  nm. Samples with metal concentrations just on the percolation threshold are formed by metal nanoparticles of 10  nm and alumina aggregates of 28  nm in diameter. The inorganic phase is homogeneously dispersed within the polymeric matrix in all investigated samples. It has been shown that the nanocomposite structure determines the oxidation behavior of Al nanoparticles within the polymeric matrix under air exposure. Results clearly show that cooperative effects arising in Al/polymer nanocomposites in the vicinity of the percolation threshold define its chemical properties. In addition, experiments show that the chemical structure of synthesized RDX and AN nanopowders is completely identical to the ordinary grade powder. Nevertheless, the burn rate value of pure RDX could be doubled if nanopowder is used instead of conventional powder.

      The solidification of energetic phases in a porous matrix (Cr2O3) was used to prepare and stabilize nanoscale explosive particles [28]. The thermochemical behavior of RDX nanoparticles strongly differs from that of micron-sized RDX. For instance, the temperature at which the decomposition occurs is significantly lowered and the melting point is removed. The effect of the decomposition of RDX nanoparticles on the matrix in which they are trapped was observed by atomic force microscopy.

      The Cr2O3/RDX nanocomposite materials were mixed with aluminum nanoparticles to formulate gas-generating nanothermites (GGNTs). The combustion of GGNTs involves a synergy mechanism in which the decomposition of RDX nanoparticles fragments the Cr2O3 matrix and primes the thermite reaction. Classical nanothermites were obtained by mixing nanoparticles (diameter <100  nm) of metallic oxides (WO3) with a metal (Al) as reducing agent. These materials were used to demonstrate that nanoparticles may (1) significantly lower the ignition delay time and (2) remarkably increase the combustion rate.

      4. Mechanisms of Nanothermite Reaction

      Nanopowders are often used to produce so-called metastable intermolecular composites (MICs). These are mixtures of nanosized reagents that are stable under normal conditions and capable of interacting with each other with the release of large amounts of energy being activated by a triggering stimulus (thermal, mechanical, or electrical). Examples of such MICs are mixtures of nanoparticles of metals such as Al, Mg, Zr, Hf, etc., and nanoparticles of metal oxides (Fe2O3, MoO3, Cr2O3, MnO4, CuO, Bi2O3, and WO3). It is known that in the case of classical thermites, the combustion reaction is slow due to the relatively slow diffusion process. When the reagents are in the nano form, the diffusion distances are much shorter and the reaction rate is increased significantly as compared with the reaction rate of conventional thermites. An area of particular interest is the use of MICs in microscale motors. This is related to the development of microscale propulsion systems and the use of these energetic materials in micromotors. Supposedly, the MICs could find application as gas-generating compositions. They can combine high-energy characteristics with unprecedented stability, safety, and an opportunity to precisely control the burning rate in a wide range through the regulation of granulometric composition. In the case of nanothermites, due to fast reactions the energy losses to the combustor wall are negligible. For example, the burning rate of MoO3–Al nanothermite, prepared by mechanical mixing of 79  nm aluminum particles and 30  nm  ×  200  nm MoO3 flakes, reached 790  m/s in a metal tube of 0.5  mm diameter. This composition is considered as a promising base for microscale rocket propellants [29]. Other possible applications of nanoscale MICs are ammunition primers and electric matches [30].

      Over the last three decades there has been significant growth in understanding the ignition and combustion mechanisms of nanothermites and other nanoenergetic materials. However, there are still many unknown issues regarding the physics and processes that control these highly exothermic reactions. The role of oxygen release from metal oxide in the phenomenon of nanothermite ignition was discussed in Ref. [31]. In that work, the advanced experimental approach has been used, and it includes simultaneous use of time-of-flight mass spectrometry, optical emission, and T-jump heating units at heating rates up to 10⁵  K/s. The reactions of type 2Al  +  3MO  →  Al2O3  +  3M  +  ΔQ were studied where MO designates metal oxide. It was found that the oxygen produced by decomposition of MO particles plays an active role in the reaction. Experiments with different oxides such as CuO, Fe2O3, and ZnO showed that the reactivity of an Al/MO pair directly depends on the capability of oxygen release from oxide particles. Therefore higher reactivity of an Al/CuO mixture can be attributed to the higher oxygen release rate as compared with the lower release rates for Fe2O3 and especially ZnO. Time-resolved mass spectrometry records of the formation of Al suboxides (AlO and Al2O) show that the reaction of Al oxidation does not follow thermal equilibrium calculations, indicating that the system is far from equilibrium. Supplementary records by high-speed X-ray movie (135,000  fps) confirm that oxygen release prior to ignition is instant, indicated by temperature measurements. In reality, ignition temperature definitely correlates with the instance of oxygen release from MO. At the same time, an original observation was made with Bi2O3. In the system Al/Bi2O3 it was recorded that nanothermite reaction starts before the oxygen is released from the neat Bi2O3. It suggests that the condensed phase reaction of liquid Al with oxygen ions was formed in melted Bi2O3 and transported to the surface of Al particles. It is stressed that these reactions may play a more significant role than was previously expected. Later on, the paper of the same authors' team published in a special issue of Combustion and Flame [32] generalized the experimental data regarding the mechanism of condensed-phase reactions of Al with different metal oxides, which proceed simultaneously with reactive sintering. As was mentioned in the Editorial Comment to this issue [33], the results available suggest that the condensed-phase reactions may be more prominent than previously thought. Additional evidence of the presence of developed condensed-phase reactions in the ignition and combustion of nanothermite materials was presented in Ref. [34,35]. A comprehensive review of the state of the art in formulating the reaction mechanism of nanothermites is presented in the review paper by M. Zachariah and G.C. Egan [36].

      The effect of aluminum particle size (108  μm–80  nm) on confined flame propagation velocities in thermite composites was investigated in Ref. [37]. In all cases, nanometric copper oxide was used as the oxidizer. It was found that the velocity exhibited two distinct regimes: between 108 and 3.5  μm the velocity scaled as the particle diameter to the (−0.56) power and became invariant in the size range below 3.5 microns.

      One explanation for the invariance is that the pressure-driven flow reaches some peak velocity, controlled by the pressure gradient, pore size, and fluid viscosity. Another explanation is that the system becomes limited by the internal gas heating rate, defined by the intrinsic kinetic time scale, and which can significantly impact the effective particle heating time.

      One open question is whether the fast reactivity is primarily an artifact of the small dimensions of the fuel, the oxidizer, or a combination of the two. The effect of Al particle size over a relatively narrow range of particle diameters between 44 and 121  nm was examined [38]. The authors showed that the flame velocity linearly increased as the metal particle diameter decreased to a size of 80  nm, then no longer varied when 44  nm Al was used. The authors suggested that this was either because of a change in kinetic mechanism, or in part because of the increased relative amount of passivating Al2O3 in the particles, which would serve as a thermal heat sink during reaction. The authors of Ref. [39] have shown that in a composite containing micron-aluminum and a nanoscale oxidizer the flame propagated faster than in a composite of nano-aluminum and a micron-scale oxidizer. The effect of oxidizer nanoscaling versus Al nanoscaling was twofold.

      Fresh results obtained experimentally and theoretically [40,41] demonstrate the fast sintering of particle aggregates into bulk alumina in conditions of fast heating rate. Thus questions are raised about effective particle size during the ignition and combustion of ensembles of nano-Al particles. The reactive molecular dynamics calculations carried out in Ref. [42] showed that upon fast heating of aluminum core/oxide shell particles the melted core Al atoms diffuse outward into the oxide shell, which is driven by an induced built-in electric field. This leads to the melting of oxide shell at temperatures much lower than the oxide melting point and to sintering of the particles due to the action of surface tension forces. Importantly, the characteristic sintering time according to calculations is even shorter than the reaction time. This may qualitatively explain why the experiment does not give an extremely short burning time for very small Al particles. Multimillion atom molecular dynamics simulations reveal the mechanism underlying higher reaction rate in a chain of aluminum nanoparticles as compared to an isolated nanoparticle [43]. This is due to the penetration of hot atoms from reacting nanoparticles to an adjacent, unreacted nanoparticle, which brings in external heat and initiates exothermic oxidation reactions. The calculated speed of penetration is 54  m/s, which is within the range of measured flame propagation rates. The results of calculations are presented in Fig 1.1.

      It was found that when the shells of outer aluminum nanoparticles melt, their penetration into respective cores starts. This results in expansion and deformation of the outer aluminum nanoparticles. This is then followed by penetration of outer atoms into the central aluminum nanoparticle. In addition to bringing in external heat via convection, already reacting aluminum nanoparticles can initiate oxidation reactions inside an adjacent, cold aluminum nanoparticle. Due to a combination of these effects the cold aluminum nanoparticles oxidize at a faster rate than an isolated aluminum nanoparticle. Finally, the proximity effect has to be given appropriate consideration when developing a theoretical model to explain the mechanism behind oxidation of aluminum nanoparticle aggregates.

      5. Nano-Explosives

      Nanostructured energetic materials are a new concept composite powder, which can dramatically improve the performance of gunpowder and explosives. The combination of nanocrystals of explosives and nanoporous substrates gives composite products of original properties and unique parameters. The following are some examples of recently reported research results obtained in experiments with nano-explosives.

      One of the first attempts to control the combustion properties of a high explosive in the nano state was reported in Ref. [44]. A porous chromium(III) oxide matrix was impregnated with RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine). The reactivity and sensitivity of Cr2O3/RDX nanocomposites were studied by impact and friction tests, differential scanning calorimetry, and time-resolved cinematography. It was found that the size of RDX nanoparticles and their distribution in the Cr2O3 matrix have an essential influence on their reactivity, which differs significantly from those of micron-sized RDX. In particular, in the nanocomposites with RDX contents between 6.2% and 80%, decomposition starts before the melting point of RDX. This means that the thermal decomposition of nanometric RDX proceeds with decreased activation energy. It was also found that for RDX contents between 14.3% and 42.0%, the nanocomposites are less sensitive to impact than pure RDX. Note that in this case the explosive layer is not continuously distributed on the Cr2O3 surface, while with higher RDX content (42.0–95.0  wt%) it covers the entire Cr2O3 surface, which results in increased sensitivity as compared with pure RDX. However, at highest RDX content (>95%) the same as pure RDX impact sensitivity has been detected. The combustion of nanocomposites with relatively low RDX content (14.3% and 25.0%) is very irregular and stops when cutting the laser irradiation. Self-sustained combustion after laser cutoff is realized for the RDX-rich nanocomposites (40%–95%). The burning rate decreases when RDX content increases.

      Figure 1.1  Snapshots of the system at different sequential stages (A,B,C, and D) of simulation. Aluminum atoms in the outer ( left and right ) aluminum nanoparticles are shown in yellow , oxygen atoms in outer aluminum nanoparticles are in red , aluminum atoms in the central aluminum nanoparticle are in green , and oxygen atoms in the central aluminum nanoparticle are shown in blue . Penetration into the central aluminum nanoparticle is observed, and the system forms an ellipsoidal aggregate by 1   ns [43] . 

      Reprinted with permission from Copyright © 2013 AIP Publishing LLC.

      RDX reactivity behavior correlates well with the morphology of explosive material distribution in the Cr2O3 matrix. At low RDX contents (<10  wt%), the resulting RDX particles are separated from one another and are typically of 10  nm size. The decomposition proceeds in one step and the composition is very insensitive to impact and friction stress. With increased RDX content (10–40  wt%), the deposited explosive particles are on the surface of the Cr2O3rods but they are still discontinuous and of nanometric size. The decomposition proceeds in two exothermic stages before an RDX melting. The combustion is not self-sustaining and there is no transition to detonation. At RDX contents between 40% and about 75%, the surface of the oxide pores is totally covered with an explosive layer. The composition undergoes a self-sustained combustion, and it can detonate in a confined space. Finally, for the higher than 75% RDX content, the explosive layer surrounds the Cr2O3 core and the properties of composition approach those of pure RDX.

      The solidification of energetic phases in a porous matrix (Cr2O3) was used to prepare and stabilize nanoscale explosive particles. The thermochemical behavior of RDX nanoparticles strongly differs from that of micron-sized RDX. For instance, the temperature at which the decomposition occurs is significantly lowered and the melting point is removed. The effect of the decomposition of RDX nanoparticles on the matrix in which they are trapped was observed for the first time by atomic force microscopy.

      Another example of the unique properties of nanostructured energetic materials has been described in Ref. [45]. It was demonstrated that a self-propagating reactive wave moving faster than 2  m/s can be realized using a 7-nm RDX annular shell around a multiwalled carbon nanotube (MWCNT). This burning rate is more than 100 times the value for bulk RDX at atmospheric pressure. It was found that the burning rate increment depends on the structure of the carbon nanotube (CNT). The effect is higher in the case of a 10 wall nanotube (22  nm tube diameter) as compared with that for a nine wall nanotube (13  nm). The reaction also creates an anisotropic pressure wave of high total impulse per mass (300  N  s/kg) and produces a concomitant electrical pulse as large as 7  kW/kg. The physical reason for unusual combustion behavior of coated CNTs is extremely high thermal conductivity of the CNT, which may reach the value of 3500  W/m  K at room temperature and is more than 80 times larger than that for the best conductor Ag (430  W/m  K).

      Unfortunately, there exist great problems with the scaling of discovered effects. With larger system sizes the effects are much less and special efforts have to be undertaken to provide practical feasibility of new phenomena. In addition, there exist technology issues because of heterogeneities in the thickness of CNTs as well as the RDX coating that lead to irregular performance along the axial position of the composites.

      The continuation and further development of this direction of research was made with a single-walled CNT (SWCNT) coated with chemically bonded energetic material [46]. Using diazonium chemistry a series of nitrophenyl-decorated CNT composites have been synthesized. The intention was to explore coated CNTs, which may release energy in a controllable manner, and to investigate the effect of thermal conductivity of CNTs on the rate of explosive reactions. It was established that diazonium chemistry is an efficient scheme to attach energetic molecules (nitrobenzenes) onto the CNT surface homogeneously with high density. It was found that chemically bonded composites release energy at low temperatures over physically mixed ones (Tmax heat release  =  373.6°C against 280.3°C) and the composites with highly conductive CNTs exhibit explosive behavior at lower temperatures. In addition, it was concluded that the better performance is demonstrated when composites are made in vertically arrayed structures with metallic conductivity CNTs.

      Some peculiar findings were made when studying the optical ignition of CNT-based composites. First, it was accidentally discovered that SWCNTs ignite when exposed to a conventional photographic flash [47]. This photoeffect occurs for SWCNTs prepared by carbon arc, laser ablation, or chemical vapor deposition upon exposure to a camera flash at close vicinity, just a few cm away from the sample. Ignition did not occur for multiwalled nanotubes, graphite powder, fluffy carbon soot, or C60. Ignition and burning occur when local increases in temperature are sufficient to initiate the oxidation of the carbon and propagate as more heat is released by this exothermic reaction. In air, the average light power needed to ignite SWCNTs was found to be 100  mW/cm² (±20  mW) for a sample density of about 0.2  g/cm³ (pulse rise time 50  μs; decay time 1.2  ms). It was supposed that the effective transient local temperature within the tubes must be at least 1500°C.

      In continuation of this work, the photoignition phenomenon of MWCNT/ferrocene mixtures by using a continuous wave (CW) xenon (Xe) light source was studied [48]. The aim was to find the power ignition threshold by employing a CW instead of pulsed Xe lamp. The luminous power thresholds for triggering ignition were found for different mixture weight ratios by varying the parameters of the CW Xe light incident on the sample, such as luminous power and wavelength range. It was found that photo-induced ignition for a 1:3 weight ratio MWCNT/ferrocene mixture (75% ferrocene by weight) is obtained with the lowest luminous power in the UV/vis range (up to 330–377  mW/cm²). In accordance with chemicophysical interpretation the irradiating light on MWCNTs/ferrocene samples produces ferrocene in the excited form capable of promoting electron transfer processes to MWCNTs. In this way, the formation of radical species, which easily react with oxygen, triggers the combustion process of the mixture.

      The phenomenon of photo-induced ignition has been employed for the initiation of explosives in Ref. [49]. For the first time, optical initiation of energetic materials via a conventional flashbulb became possible on a large surface area. It is believed that the mixtures of explosives with SWCNTs may become candidates for remote optical triggering of safety apparatus, such as the firing of bolts on space shuttle rockets and aircraft exit doors, and for controlled burning of explosives. Experimentally, with use of a common electronic strobe of flash photography (Albinar 120MDT-TZ with 5600  K of color temperature), the samples were flashed with various combinations of conventional explosive pentaerythritol tetranitrate (PETN) and commercially obtained SWCNTs (as produced from raw high-pressure carbon monoxide from Carbon Nanotechnologies, Inc., with at least 29% per weight iron impurity). In air, the average light power output needed for the combustion initiation of 1:1 mixture was 17  W/cm² with a flash duration time of 1–2  ms. In further experiments with K-6 cyclic dinitrourea explosive loaded into a copper cylinder and loosely packed SWCNTs added on top (Fig. 1.2) of the K-6 (approximate density of 1.0  g/cm³), exposure by flashbulb (duration time 3  ms, the light power W/cm²) resulted in initial deflagration of K-6 followed by a detonation process with an average speed of 6.8  km/s. It is stated that while much is known about the physical properties of nanotubes, it is believed the impurities in CNTs (e.g., iron, nickel) can serve the ignition reaction sites. Investigation of its role would be the subject of future studies.

      Original attempts at using MWCNTs as support for incorporating polynitrogen N8 were made in Refs. [50,51]. N8 possesses giant heat of formation, Hf  =  +3630  cal/g, exceeding greatly that of the best explosives (HMX  ∼+91  cal/g). It is a known fact that pure polynitrogen systems are metastable but advanced theoretical studies showed that when the polymeric nitrogen chain is encapsulated in a CNT, it can be stable at ambient pressure and room temperature, which makes such composites promising nanoscale energetic material. Clear evidence of the presence of polynitrogen atoms in CNTs is not yet available. According to the experimental data of [50] the content of nitrogen atoms in CNTs can vary in the range 1.7%–4.0%, and nitrogen exists in the form of pyridine-like, graphite-like, oxidized nitrogen and a nitrogen physisorption layer. Based on the results of experimental studies, it is stated that it is possible to obtain nitrogen-doped CNTs with controlled concentration and structure. This may provide the development of novel nanoenergetic materials.

      Figure 1.2  Assembly of a copper cylinder and a funnel containing K-6 explosive prior to addition of 0.020   g of a single-walled carbon nanotube and irradiation with a flashbulb. Pins surrounding the cylinder measure shock wave arrival time [49] . 

      Reprinted with permission from Copyright © 2005 American Chemical Society.

      Porous silicon was discovered first as a reactive material when it

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