AL-FARABI KAZAKH NATIONAL UNIVERSITY and INSTITUTE OF COMBUSTION PROBLEMS Z. A. Mansurov A. S. Mukasyan A. S. Rogachev SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS Textbook Almaty «Qazaq University» 2018 UDC 544.1 (075.8) LBC 21.1 я 73 M 24 The Academic Council of Department Chemistry and Chemical Technology and RISO of al-Farabi Kazakh National University was recommended for publication (Protocol №7 dated 05.07.2018) Reviewer Doctor of Chemical Sciences, Associate Professor N.N. Mofa We express great gratitude to Dr. S.M. Fomenko for discussion and thanks to Ph.D-student Makpal Seitzhanova for her assistance in preparation of this textbook for publication. Mansurov Z.A., Mukasyan A.S., Rogachev A.S. M 24 Self-propagating high-temperature synthesis: textbook / Z.A. Mansurov, A.S. Mukasyan, A.S. Rogachev. – Almaty: Qazaq University, 2018. – 164 p. ISBN 978-601-04-3469-1 The textbook is devoted to the problems of self-propagating high-temperature synthesis. This textbook can be useful to a wide range of professionals involved in nanotechnology as well as bachelors, masters and Ph.D students and doctors. Published in authorial release. UDC 544.1 (075.8) LBC 21.1 я 73 ISBN 978-601-04-3469-1 © Mansurov Z.A., Mukasyan A.S., Rogachev A.S., 2018 © Al-Farabi KazNU, 2018 2 C ONTENTS PREFACE ............................................................................................................................... 5 Chapter 1. SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS ................... 7 1.1. General definitions ...................................................................................... 7 1.2. Fundamentals of SHS .................................................................................. 8 1.3. Structural macrokinetics of SHS processes ................................................. 10 Control questions ................................................................................................... 11 References ............................................................................................................. 11 Chapter 2.DIFFERENT PROCESSES OF SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS ............................................................. 12 2.1. Gasless combustion synthesis ...................................................................... 12 2.2. Combustion synthesis in gas–solid systems (infiltration combustion) ......... 15 2.3. Combustion synthesis with a reduction stage .............................................. 20 2.4. Solution combustion synthesis .................................................................... 22 2.5. Mechanical activation of initial powder mixtures for SHS .......................... 23 2.6. Example of SHS with preliminary mechanical treatment of the powders ... 25 Control questions ................................................................................................... 26 References ............................................................................................................. 26 Chapter 3. THERMODYNAMICS AND DRIVING FORCE OF SHS PROCESSES ..... 30 3.1. General principles ........................................................................................ 30 3.2. Equilibrium, reversibility, stationary and stability of the SHS processes and products ........................................................................ 36 3.3. The thermodynamics of the reaction cell ..................................................... 38 Control questions ................................................................................................... 41 References ............................................................................................................. 41 Chapter 4. KINETICS OF HETEROGENEOUS REACTIONS ........................................ 42 4.1. Solid-state reactions ..................................................................................... 44 4.2. Solid–gas reactions ...................................................................................... 49 4.3. Reactions with the liquid phase ................................................................... 57 4.4. Reactions with gasification of the initial solid phase reagent ...................... 58 4.5. Methods of high-temperature kinetics of heterogeneous reactions .............. 60 Control questions ................................................................................................... 64 References ............................................................................................................. 65 Chapter 5. STRUCTURE FORMATION IN HYBRID SOLID–GAS SYSTEMS ............ 68 5.1. Model of structure formation during combustion of metals with nitrogen ........................................................................................................ 70 5.2. Models of structure formation during combustion of non-metals in nitrogen ................................................................................................... 73 Control questions ................................................................................................... 77 References ............................................................................................................. 77 3 Chapter 6. SHS OF TiB2-Al2O3 and CrB2-Al2O3 CERAMICS ........................................... 78 6.1. Self-propagating high-temperature synthesis of boron containing ceramic materials: the state of art ................................................................ 78 6.2. Experimental ............................................................................................... 81 6.3. Results and discussions ............................................................................... 84 6.3.1. Layer-by-layer X-ray structural analysis of hardened samples. SHS-process was stopped by “Hardening” method followed by analysis of partially and completely burnt part of the charge in 0.75TiO2-0.25Ti-2B-Al system ............................................................... 84 6.3.2. SHS parameters ........................................................................................... 85 6.3.3. Analysis of the composition and morphology of the combustion products ....................................................................................................... 87 6.4. Conclusions ................................................................................................. 91 Control questions ................................................................................................... 91 References ............................................................................................................. 92 Chapter 7. SOLUTION COMBUSTION SYNTHESIS ....................................................... 94 7.1. Synthesis gas production on glass cloth catalysts modified by Ni and Co oxides .............................................................................................. 94 7.2. Synthesis of catalysts ................................................................................... 95 7.2.1. Study of the catalytic activity ...................................................................... 96 7.2.2. Physicochemical examination of samples ................................................... 96 7.3. Characteristics and properties of the catalysts ............................................. 97 7.4. The catalytic activity of samples in the reaction of dry reforming of methane ................................................................................................... 101 Control questions ................................................................................................... 104 References ............................................................................................................. 104 Chapter 8. COMBUSTION SYNTHESIS OF SILICON AND SILICON CARBIDE NANOPOWDERS ............................................................................ 106 8.1. Combustion synthesis of silicon nanopowders ............................................ 106 8.2. Investigation of the silicon nanopowders .................................................... 108 8.3. Combustion synthesis of silicon carbide ...................................................... 113 Control questions ................................................................................................... 117 References ............................................................................................................. 118 Chapter 9. SHS REFRACTORY MATERIALS “FURNON” AND THEIR PRACTICAL IMPLEMENTATIONS IN KAZAKHSTAN AND RUSSIA ... 119 9.1. SHS-refractories: “Furnon” ......................................................................... 119 9.2. New carbon-containing refractories ............................................................. 123 Control questions ................................................................................................... 132 References ............................................................................................................. 132 Laboratory work 1. Measuring of the combustion wave velocity ............................................ 134 Laboratory work 2. Measuring of the maximum combustion temperature .............................. 140 Laboratory work 3. Combustion wave profile ......................................................................... 151 Laboratory work 4. SHS of nitrogen containing materials by using chromium oxide based concentrate ............................................................................................................ 157 Laboratory work 5. Synthesis of the boron-based composites by using SHS method .............. 160 Laboratory work 6. SHS synthesis of superconductors: magnesium diboride ........................ 162 4 P REFACE Self-Propagating High-Temperature Synthesis,сombustion synthesis is an attract- tive technique to synthesize a wide variety of advanced materials including powders and near-net shape products of ceramics, intermetallics, composites, and functionally graded materials. SHS-produced materials have found their application in different branches of modern science and technology, including mechanical engineering, aerospace engineering, electrical engineering, chemical industry, ferrous and nonferrous metallurgy and electronics. Self-propagating high-temperature synthesis is a subject of discussion on different international symposiums and meetings on combustion, as well as materials science forums, where different aspects in the field of SHS are regularly presented and discussed. It is worth noting that a major contribution to the investigation of SHS processes was made by A.G. Merzhanov and members of his scientific school, such as V.M. Shkiro, I.P. Borovinskaya, and Yu.M. Maksimov, as well as by the world recognized leaders in the SHS field, including Z. Munir, K.C. Patil, A. Varma, T.P. Weihs and other researchers. Theory of this process is based on the classical fundamental works of N.N. Semenov, Y.B. Zeldovich and B.I. Khaikin. This textbook is written on the base of special course delivered to PhD-students of Department of Chemical Physics and Materials. In the first chapter, we consider the fundamentals of self-propagating high-temperature synthesis and structural macrokinetics of SHS processes. Chapter 2 is devoted to the different routes of self- propagating high-temperature synthesis, including gasless combustion synthesis, combustion synthesis in gas-solid systems and with reduction stage, solution combustion synthesis, mechanical activation of initial powder mixtures for SHS and the effects of mechanical treatment of the reaction mixtures on SHS. In the third chapter, we describe the thermodynamics and driving force of SHS processes, their general principles, equilibrium, reversibility, stationary and stability of the SHS processes and products, the thermodynamics of the reaction cell. Chapter 4 is dedicate to the kinetics of heterogeneous reactions, including solid-state and solid–gas reactions, reactions with the liquid phase, reactions with gasification of the initial solid phase reagent. The fifth chapter describes the structure formation in hybrid solid–gas systems, focusing on general models of structure formation during combustion of metals and non-metals in nitrogen. Chapter 6, describes the specifics of self-propagating high temperature synthesis and structure formation of boron containing, ceramics. The seventh chapter considers the solution combustion synthesis of catalysts. It is demonstrated that fine catalysts fabricated by SHS method can be effectively used for the solution of ecological 5 problems in processes of CO and hydrocarbon combustion, as well as for the utilization of the components, which lead to the, so-called, “greenhouse effect”. Chapter eighth is dedicated to combustion synthesis of silicon nanopowders. In the ninth chapter we overview the SHS refractory materials from “Furnon” family and their practical implementations in Kazakhstan and Russia. At the end of this textbook, we also provide the laboratory works that are related to the different aspects of SHS process. Finally, for those who seek for the deeper understanding of the theory and mecha- nisms of SHS-processes, as well as other combustion-based technologies, we highly recommend reading additional literature cited in this book (cf. Chapter 1, Ref. 1-10). 6 C 1 HAPTER SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS 1.1. General Definitions Self-propagating high-temperature synthesis (SHS) is a science-intensive process for fabrication of materials. It was established in the second half of XX century by group of Russian scientists leaded by A.G. Merzhanov [1]. The history of this discovery and development of its technological applications have been described in many books and reviews [2-6]. Comprehension of SHS requires fundamental knowledge in thermodynamics, chemical kinetics, general and structural macrokinetics, materials science, and other related fields. SHS involves processes in which the reactive mixture of the initial reagents (usually powders), when ignited, spontaneously transformed into the valuable solid products due to the exothermic self-sustained reactions. Several other terms – such as combustion synthesis, gasless combustion, self-propagating exothermic reaction – are used to describe the process. A well-known example of SHS reaction is the thermite reaction given below: Fe O + Al → 2Fe + Al O 2 3 2 3 This reaction generates temperatures above the melting point of alumina and is used in the welding process for joining railway lines. Considering the SHS as a variety of heterogeneous combustion, three stages of the process can be outlined: 1) mixing the components typically at room temperature, when the chemical reaction does not yet take place; 2) the initiation of an exothermic chemical reaction (ignition or self-ignition); 3) a self-sustaining chemical reaction which occurs without external heat sources and leads to the formation of combustion products (chemical compounds, powders, materials or net shape articles important from the practical applications) [4, 7-9]. The initiation of a chemical reaction is usually carried out by heating the reaction mixture and there are two entirely opposed methods of heating. The first way is to heat the whole sample slowly so that temperature has time to equalize over the entirety of its volume. In this case the reaction should develop simultaneously and uniformly at all points of the sample and at a specific temperature one should observe a sharp self- 7 acceleration of the process – the whole sample evenly ‘self-ignites’. This SHS mode is called volume combustion or thermal explosion, it is illustrated in Fig. 1.1. SHS in the thermal explosion mode has much in common with reaction sintering in powder tech- nology, but there is a fundamental difference. It consists in the fact that in reaction sintering it is necessary to avoid spontaneous heating of the sample by chemical reac- tion, whereas in SHS this warm-up is utilized. The theory of thermal explosion was developed in the works of the outstanding Russian scientist and Nobel Prize winner N.N. Semenov and his followers. Fig. 1.1. Self-propagating high-temperature synthesis modes: volume combustion. The second way of ignition is optimal rapid heating of only a small volume of the sample (e.g. ~1 mm3) that results in local reaction initiation of an exothermic reaction, which then self-propagates to the rest of the sample in the form of a combustion wave. This SHS mode is called the wave or auto-wave combustion mode. Fig. 1.2 shows schematically such a process. Fast heating is needed to ensure that the heat from the local area of ignition has no time to spread to nearby areas and create an uneven temperature distribution in the sample. The point is that the route of the reaction and thus the properties of the combustion products depend on the initial temperature of the medium. Consequently, if the initial temperature is not uniform, the products of combustion synthesis are varied in the volume of the sample. Typically, the non- uniformity of the product is undesirable, except in special cases where the purpose of synthesis is to provide materials with a gradient structure and properties. Fig. 1.2. Self-propagating high-temperature synthesis modes: auto-wave combustion. 1.2. Fundamentals of SHS Theory has played an important role in combustion science. Early examples, include Chapman-Jouguet detonation theory; the Burke-Schumann fast-chemistry approxi-mation for diffusion flames (derivable in a limit process that called 8 Damkohler-number asymptotic); Frank-Kamenetskii's steady-state theory of spontaneous combustion (the origin of activation-energy asymptotic); Zeldovich's early contributions to deflagration theory (equivalent to use of activation-energy asymptotic for achieving spatial scale separation); and the Darrieus-Landau hydrodynamic limit for deflagrations (which could be termed Peclet-number asymptotic). It is no an accident that most of these theoriespresent anasymptotic approxima- tions. Indeed, the combustion problems, like those of fluid mechanics, can seldom be linearized, and so analytical strategies require mathematical tools capable of dealing" with nonlinearities. Asymptotic is the only universal tool, requiring only a large para- meter Asymptotic, whether matched asymptotic expansions (such as boundary-layer theory), Poincare-Lighthill strategies (as in perturbed orbital mechanics and sonic- boom theory) or multiple-scale techniques (justifying Krylov-Bogoliubov averaging, WKB approximations, and adiabatic invariances), essentially emerged strongly after World War II (although with roots extending back to Laplace and Newton) and was vigorously developed by the fluid-mechanics community. It is difficult to pick up copies of the Journal of Fluid Mechanics from the 1950s, 1960s, and 1970s, and understand the theoretical work discussed there without at least a rough grasp of asymptotic. In combustion, the development of asymptotic was slower and for many years was restricted to the Russian school associated with names of Semenov, Zeldovich, and Frank-Kamenetskii. The achievements of this school are summarized by Zeldovich, Barenblatt, Librovich, and Makhviladze in a book [10], which in many ways is a compendium of that work. These contributions are characterized by rich physical discussion, and they challenge anyone who might feel that physical understanding and intuition are necessarily in conflict with formal mathematical strategies. It is a fact that simple mathematical models that incorporate a minimum of physics, when solved in a manner that makes transparent the physical interactions in various parts of the combustion field, and when the results are presented in a physical context, can be a source of physical insight superior to any other. It is difficult, for example, to see the specific role of radiation in the stabilization of flame balls [11] without an examination of the mathematical stability theory. In fact, a little thought along the lines of radiant-loss influences on flame speeds, without carefully considering Lewis-number effects, can easily lead to an apparently plausible, but incomplete and possibly misleading picture. However, the Russian school may have had one flaw, i.e.an apparent unwillingness, once the mathematical model was posed, to push analysis to the limits. Some hint of why this had happened can be found on page 369 of [10], which suggests that additional details may have little physical validity. But, in fact, there is no reason to believe that the omitted physics necessarily would undo the subtle details predicted by the physics that is retained. Thus, a legitimate strategy is to push the mathematics to the limit, but be prepared to adjust the model should the solutions be at variance with the experimental record or fully detailed numerical solutions. Flame balls provide one example of rich behavior generated by a simple model consistent with the experimental record: there is a lean flammability limit [11]; one- dimensional stability only if heat losses by radiation, convection or conduction are present [12,13]; the disappearance of an interval of stable solutions as the Lewis number of the deficient reactant is increased from small values to unity [14]; three- dimensional instabilities at mixture strengths well removed from the lean limit [15]; 9 repulsion of one flame ball by another to generate drift [16]; and stabilization by fluctuating velocity gradients of appropriate amplitudes and frequencies [17]. The theoretical papers in the Journal of Fluid Mechanics today look quite different from those of fifty years ago. These days, the applied mathematician wrestling with mechanics problems is far more likely to use scientific computation strategies than asymptotic. The same trend is now apparent in combustion (albeit this review contains counterexamples), naturally so since asymptotic has its limitations. In combustion, most asymptotic treatments are either one-dimensional or small perturbations thereof; exceptions include descriptions of the dynamics of combustion fronts for flames (such as the Michelson-Sivashinsky equation or the Kuramoto- Sivashinsky equation) or more recently for detonations, in which multidimensional combustion problems are reduced to a partial differential equation or an integral differential equation for a single scalar, an equation that must be solved numerically, for the most part, but a numerical task that is much simpler than the unreduced problem. It must be emphasized that the trend towards computation is not simply an aban- donment of analytical strategies for computational approaches of a kind long pursued in the past. Typically, the models are still incomplete, the algorithmic investment is comparatively small, and there is an applied-mathematician's sensibility (for good and bad) that permeates the endeavor. Recent monographs and review articles [18,19] summarize many of the main achievements in combustion theory over the past fifty years. This literature documents attainment of rather a high level of conceptual coherence. Combustion theory is, in fact, perhaps one of the most elegant areas of classical phenomenology, presenting a graphic example of the wide range of natural phenomena that can be deduced from a few fundamental principles [20]. 1.3. Structural macrokinetics of SHS processes In recent years strict requirements demanded by modern materials led to intensive studies of structures and mechanism of structure formation of the SHS products. This is not accidental since the structure of a materialto a great extent determines its properties, especially. It would not be overestimation to state that problem of controlling product structure is one of the most important tasks in further development of SHS. Here the structure means a wide range of characteristics including macrostructure (composition distribution, macroscopic defects), microstructure (arrangement of phases and crystals with respect to each other, grain size, porosity and pore structure, localization of impurities), and crystal structure (crystal lattice type and lattice parameters, presence of defects, ordering with formation of super lattices, amount and distribution of dislocations). The structure of combustion wave itself needs to be added to the above classification since distribution of temperature and concentration in the combustion and after-burning zones markedly affects the composition and structure of the synthesized materials. It is well recognized that structural macrokinetics (SMK) studies evolution of structure in the course of chemical transformation taking into account heat and mass transfer processes [7,8]. A place of SMK in the number of other fields of science can be presented by the following equations: 10