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The chemistry of self-propagating high-temperature synthesis

Alexander G. Merzhanov
Institute of Structural Macrokinetics and Materials Science, Russian Academy of Sciences, Chernogolovka, Moscow, 142432 Russia. E-mail: merzh@ism.ac.ru
Received 28th January 2004, Accepted 16th March 2004 First published as an Advance Article on the web 27th April 2004

The chemistry of SHS is briey reviewed and illustrated by some examples of the practical implementation of SHS-produced powders, ceramics, hard alloys, cast materials, and items. Outlined are some promising lines of further R & D in the eld.

1 Introduction
The processes leading to the formation of materials as a product of a reaction are numerous. Examples of these are trivial furnace processes in the solidsolid, solidgas, and gasgas systems carried out at a constant or increasing temperature, plasmo-chemical synthesis, reactions in shock and detonation waves, etc. Among these, a worthy position is occupied by the so-called Self-propagating High-temperature Synthesis (SHS, also known as combustion synthesis, or synthesis by combustion). SHS can be performed in a system reacting in the mode of wave propagation due to heat transfer from hot products to cold reagents after local initiation (ignition) of the process. In the typical frames of SHS, three main stages of the process ignition, front propagation, and product cooling are clearly seen (Fig. 1). The typical characteristics of SHS are presented in Table 1. Note that the maximum combustion temperature T m, the velocity of front propagation U , and the heating rate may attain very high values, which allows one to consider SHS as an extreme chemical process.

DOI: 10.1039/b401358c

Alexander Merzhanov started his research work in 1954 at the Institute of Chemical Physics, Moscow. In 1960, he moved to the branch of this institute in Chernogolovka, Moscow suburb, and became head of the Laboratory on Ignition Processes and then a supervisor of the Division of Macrokinetics. He is currently a director of the Institute of Structural Macrokinetics and Materials Science in Chernogolovka, founded by him in 1987. In 1997, he was elected a member of the Russian Academy of Sciences. His scientic activity is concentrated on general and structural macrokinetics, combustion theory and nonlinear dynamics, selfpropagating high-temperature synthesis (SHS), and chemistry and technology of materials. He is an organizer of seven international symposia on SHS and the general editor of the International Journal on SHS (Allerton Press, New York). For the period of 20022004, he was elected as president of the Advisory Board of the World Alexander G. Merzhanov Academy of Ceramics.

The SHS method was developed on the basis of a scientic invention. In 1967 at the Branch of the Institute of Chemical Physics of the USSR Academy of Sciences in Chernogolovka (a small town not far from Moscow), a new type of reaction between solid reagents in the mode of combustion yielding solid products was discovered in a search for new models of combustion in condensed media. Later this process was called the Solid Flame Phenomenon (SF); however, it was ofcially registered as The Phenomenon of Wave Localization of Autoretarding Solid-Phase Reactions.1,2 Discovery of SF was a very important step in the development of combustion theory. Numerous scientic directions were developed on the basis of SF studies. Among these, the following are of special interest: non-equilibrium theory of ame propagation3 (which gave explanation to the SF phenomenon), the theory of inltration-aided combustion,4,5 the theory of heterogeneous combustion,6 and experimental diagnostics and modeling studies of unsteady combustion (front auto-oscillations, spinning waves, chaos).7,8 In these processes and theories, the formation of solid products is of signicant importance. Work in the area of SHS was started after the discovery of the SF phenomenon by using the same materials, mixtures of metals with boron, carbon, and silicon. At the rst stage of the research, SHS was closely associated with the discovery and the terminology of combustion sciences was widely used, giving SHS another name: Combustion Synthesis. Later, the range of the combustion systems, conditions, and tasks was broadened, and this resulted in further development of SHS as a separate branch of combustion sciences,

Fig. 1

Still frames of the combustion process.

Table 1 Typical characteristics of the SHS process Particle size, r/mm for metals for non-metals Relative density, D Diameter, d/mm Length, L/mm Initial temperature, T 0/K Gas pressure, P/MPa Combustion rate, U /cm s21 Combustion temperature, T m/K Heating rate, W /K s21 /kJ cm22 s21 Igniting ux, q Induction period, tign/s Ignition temperature, T ign/K

5100 0.1 0.30.6 520 (25)d 300700 0.115 0.120 23003800 103106 42840 0.21.2 8001200
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This journal is The Royal Society of Chemistry 2004

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independent of the SF direction. The remarkable features of SHS as a method for material synthesis also promoted vigorous development of the area. The main feature of SHS is a very short time required for attaining high combustion temperatures due to heat released during exothermic reactions. This feature explains other specic characteristics, such as the high degree of conversion, partial self-purication from impurities, and the feasibility for the direct synthesis of items with a desired structure and even shape, size, and service parameters. Nowadays, not only solid ame processes are regarded as SHS, but also any material-forming combustion processes involving reagents of various nature. In the 1970s, the fundamentals of SHS chemistry were laid down by the studies carried out by Borovinskaya9,10 and coworkers, and then developed by Dolukhanyan11 (synthesis of hydrides), Kazarbina, Maximov and co-workers12 (synthesis of complex suldes), Itin and Naiborodenko13 (synthesis of intermetallides), Vereshchagin and Sviridov,14 Merzhanov and Nersesyan,15 Parkin and co-workers16,17 (synthesis of complex oxides), Patil et al.18,19 (nanopowders of complex oxides), Pampuch,20 Puszynski21 (synthesis and processing of ceramics), Boldyrev et al.,22 Holt et al.,23 Bernard and Gaffet,24 and Borovinskaya and Ponomarev25 (time-resolved XRD studies). The goal of this paper is not a comprehensive review of the state-of-the-art in the area but to present the authors understanding of the subject as well as to give some interesting examples from the work experienced.

2 Fundamentals of SHS chemistry

In this section, we will focus our attention on: . the scope of SHS reactions and choice of reagents; . the synthesis conditions that ensure a high quality of products; . the mechanism of chemical reactions in the combustion wave; . the range of SHS-produced materials; . the features of structure and chemical properties of SHS products (in comparison with existing analogs). It should be noted that the chemical nature of SHS reagents is of no importance; a decisive role is played by some formal relations between the rates of heat evolution and heat transfer in the system. The SHS theory distinguishes between the primary, macrokinetic approach and the secondary, chemical one. The former is important for appropriate performance of SHS while the latter is helpful for its optimal application to solve a specic chemical and/or technological task. 2.1 Some general information As was mentioned above, heat release during reactions and heat transfer from warmed-up zones to cold ones generate the reaction wave propagating though the charge towards the reagents and leaving the products behind. Following ref. 26 let us outline some features of the character, conditions, and patterns of wave propagation, wave structure, and combustion mechanism which are useful for better understanding of the macrokinetics and chemistry of SHS. The velocity of combustion front propagation may be either independent of (constant, which characterizes steady combustion) or dependent upon the time and/or coordinates. The latter situation takes place when the steady combustion transforms into an unsteady one. The steady combustion is considered to be preferable for material synthesis; however, frequently the non-uniformity of combustion does not affect the product quality. The combustion wave represents an expanded zone comprising a set of subzones. Each subzone is characterized by processes occurring in it. A typical SHS wave consists of preame,
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main heat release, afterburning, structure formation, and cooling down subzones. In the preame subzone (characterized by a high thermal gradient), intense heat exchange takes place though main chemical reactions do not occur. In this subzone, phase transformations and side reactions can take place. In the main heat release subzone, the main reactions occur. According to the modern combustion theory, the velocity of combustion front (the front part of the combustion wave) propagation is determined by the heat release and heat transfer in the main heat release and preame subzones correspondingly. If the heat losses from the main heat release subzone are signicant, combustion might be quenched. If the reaction occurring in the main heat release subzone is not complete, the area of afterburning (where the processes do not affect the wave propagation) can be distinguished in the main heat release subzone. The presence of the structure formation subzone is characteristic of SHS. A number of processes (crystallization, recrystallization, product condensation, phase transformation, etc.) taking place in this subzone do not affect the combustion wave velocity but strongly inuence the structure of the product. In this subzone, the product starts to cool down and is completed in the next zone the cooling down subzone. The main parameter of the SHS process is the maximum combustion temperature T m, which affects the combustion front velocity and the structure of the product. T m can be controlled by introduction of an inert diluent into the charge (decreasing T m) or by preliminary warming-up of the charge (increasing T m). Normally, SHS is carried out in mixtures of ne powders (particle size 0.110 mm), in pelleted samples (relative density up to 0.50.6) or in small samples (e.g. cylinders 515 mm in diameter). A high rate of SHS can be attained for porous samples placed in an atmosphere of gas reactant (e.g. a pellet of Ti powder in nitrogen gas). In this case, characteristics of gas reagent inltration into the sample pores (making the SHS mechanism more sophisticated) are of importance. Recently, SHS has been carried out in thin (nanosized) lms.27,28 2.2 Ideology and methodology of SHS research Based on a special ideology, SHS differs from other methods of synthesis. The most attractive features of SHS as a method for the preparation of materials and compounds are as follows: . SHS can be carried out by using relatively simple facilities or even in open air; . sometimes (but rarely), a good practical result can be obtained without having any detailed information about the process; . the process parameters can be roughly estimated by performing thermodynamic calculations; . the parameters of SHS can be determined by measuring the values of the velocity of the front propagation, the maximum combustion temperature, the extent of conversion g, the chemical/ phase composition, the amount of impurities, and some structural data as a function of reagents particle size, charge density, sample size, initial temperature, ambient gas pressure, etc.; . the quality control requires a profound knowledge of the structural macrokinetics, a novel area of research, which considers the positive and negative nonlinear feedback between the rates of chemical reactions, structural transformations, and heat/mass transfer processes; . in most cases, controlling the parameters of the end product is a major task objective of these studies. The presented ideology and methodology of SHS research have not been completely applied in practice. In some cases, the studies were limited by thermodynamic analysis and experimental diagnostics of the combustion products with determining only the main parameters of the process.

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2.3 Chemical classes of SHS reactions The chemistry of combustion originally dealt with thermal decomposition and oxidation of propellants. The objectives of SHS chemistry are more diverse. A main task objective to synthesize material rather than to increase the caloricity of the starting system opens up wide horizons for the creative fantasy of chemists. As a result, combustion chemistry has been enriched in the reactions that earlier were regarded as having nothing in common with combustion. Let us mention some of the most popular types of chemical reactions. Here the palm of supremacy belongs to the reactions of direct synthesis from the elements, such as the combustion of metals in oxygen (known since the Berzellius times) and the reaction of metals with boron, carbon, nitrogen, and silicon. Later, SHS reactions were carried out through reaction of metal with metal (synthesis intermetallides) and that of metal with hydrogen, phosphorus, sulfur, selenium, etc. The reactions of direct synthesis from the elements greatly contributed to development of combustion chemistry as a whole. Another line of research that links combustion and concomitant chemical reactions is metallothermy. Metallothermic reactions, discovered by N.N. Beketov and V.M. Goldschmidt back in the 19th century, have got the second wind in SHS research. Special interest claimed the synthesis from refractory oxides rather than from the elements. As a matter of fact, SHS combines the metallothermic reduction of the elements from their oxides and subsequent reaction between the reduced elements. An original scheme for the synthesis of complex oxides is based on the reaction between simple oxides that is being used in furnace technology. In SHS technology, one of the oxides is replaced (partially or completely) by a respective oxide-forming metal, while the process is carried out under oxygen (or in air). The system becomes combustible, and, as a result, the SHS reaction yields a mixture of oxides at a sufciently high temperature. This scheme has been used to synthesize high-T c superconductors,29,30 ferrite powders,31 etc. 2.4 Choice of reagents. Thermodynamic calculations The synthetic potential of SHS can be evaluated by using three approaches: empirical, thermodynamic, and macrokinetic. The empirical one is based on intimate knowledge of chemistry as well as on experience in the eld of SHS practice. The thermodynamic approach requires calculation and analysis of the adiabatic combustion temperature T ad and the equilibrium composition of the products at this temperature. The analysis of these data cannot give the nal answer if SHS can be performed in the system under consideration or not, but they are very valuable for coming to a proper decision. There are two methods for thermodynamic analysis of combustion: simplied and complete. In the simplied method, the adiabatic combustion temperature T ad is calculated under the assumption that the product composition is known (given). According to refs. 32 and 33, T ad can be calculated as Qeff Tad ~T0 z  c where Qeff ~Q{
n X i ~0

In these calculations, it is important to properly take into account the inuence of phase transitions (caloric effect, heat capacity, temperature). If the combustion temperature coincides with the temperature of phase transition T ph, the proportion of the high-temperature phase mph in the products can be determined as Qeff { c Tph {T0 ph ~ Lph The complete method of thermodynamic analysis34 allows calculation, not only of the adiabatic combustion temperature T ad, but also of the equilibrium composition of the products at this temperature. This method is especially important for multicomponent systems when the product composition can hardly be predicted. The results of the thermodynamic calculations for the TiO2B2O3Mg system (Fig. 2) is interesting from the practical point of view (synthesis of refractory TiB2 materials) and can be taken as an example.35 Here, the target product is TiB2 and the major side product is MgO. The calculation also predicts the presence of other side products: TiOx, MgB2, TiB, and Ti. Shadowed is the area within which only the major products, TiB2 and MgO, are formed. Note that the stoichiometric point for the reaction TiO2 1 B2O3 1 5Mg A TiB2 1 5MgO is outside this area. This implies the fact that the simplied approach to SHS in sophisticated systems may lead to a wrong decision concerning the optimal composition of the charge. In the macrokinetic approach, the kinetics of heat release in the combustion wave and heat losses are taken into consideration, which allows one to determine whether SHS can occur in the given medium or not. However, it can hardly be used in practice because of the absence of the kinetic and thermophysical data for high temperatures.

2.5 Chemical mechanism of SHS The chemistry of SHS aims at elucidating the mechanism of chemical reactions within and behind the wave, and the type of intermediates and their role in the reactions. Such work was initiated in 1975. The combustion of Ta in nitrogen was found36 to proceed in two stages: Ta ? Ta2 N reaction zone Ta2 N ? TaN subzone of afterburning
N2 N2

Liph

is the effective heat release in the reaction, and  c~Tad {T0 {1

T ad T0

C T dT
Fig. 2 Phase diagram for the combustion products formed in the TiO2B2O3Mg system (taken from the ISMAN-THERMO database).
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is the mean heat capacity of the product in the range T 0T ad.

The burning velocity is controlled by the former reaction while the product composition (partially, its structure) is controlled by the latter. In particular, the latter reaction denes the crystal modication of the product. In some cases, the product acquires a hexagonal structure whereas in others (at higher pressures) it acquires a cubic structure. Moreover, variation in afterburning conditions afforded the synthesis of Ta5N6. More profound investigation has been carried out for the reaction yielding yttrium barium cuprate, a well-known highT c superconductor,37 according to the scheme29 3Cuz2BaO2 z1=2Y2 O3 ? YBa2 Cu3 O7{x The microphotographs of the synthesized cuprate are given in Fig. 3. Since this reaction is relatively slow, the authors could identify some intermediate products and suggest the following reaction scheme:30 2Cu ? Cu2 Oz1=2O2 ?2CuO BaO2 uBaOz1=2O2 fBaO2 zBaOgmelt z2Cu2 O?2BaCu2 O2 fBaO2 zBaOgmelt z2CuO?2BaCuO2 BaCuO2 zCuO?2BaCu2 O2 z1=2O2 2BaCu2 O2 zCuOz1=2Y2 O3 ?YBa2 Cu3 O6zs zCu2 O 2BaCuO2 zCuOz1=2Y2 O3 ?YBa2 Cu3 O6zs YBa2 Cu3 O6zs ? YBa2 Cu3 O7{x The properties of YBa2Cu3O7 2 x (in particular, its T c) were found to be strongly dependent upon a value of x. Owing to special efforts, a product with a stable value of x ~ 0.08 was prepared, which ensured the stability the of product properties (see the review in ref. 30).
Fig. 4 Kinetics of the phase transformations taking place during SHS in the 3CuAl system as obtained by TRXRD.
O2 O2 O2

(1) Reactions involving no intermediates: TizC?TiC Zr ? ZrN (2) Reactions involving one intermediate product: TazC?0:5Ta2 Cz0:5C?TaC NbzB?0:5NbB2 z0:5Nb?NbB (3) Reactions involving several intermediates: 2TizC ? TiCzTiN?Ti2 CN
N2 N2

Fig. 3

Microphotographs of a sintered cake at different magnications.

Synthesis of YBa2 Cu3 O7{x (4) Branching reactions:

A new impetus to further progress in the SHS chemistry was given by the use of synchrotron radiation for time-resolved X-ray diffraction analysis (TRXRD)2224 which allows the kinetics of phase/composition transformations during SHS to be followed. The time resolution of modern facilities of this type attains a value of 510 ms, which makes this technique applicable to rapidly burning SHS systems (U 15 cm s21). For slower processes, Ponomarev and co-workers25 developed a laboratory-scale experimental setup for TRXRD based on a standard diffractometer equipped with the appropriate accessories. As an example, Fig. 4 shows the time-resolved diffraction patterns obtained during SHS of the CuAl system. Here, the formation of stable intermediate Cu9Al4 is worth mentioning. This observation suggests that: (1) the expected Cu3Al is formed behind the combustion wave, and (2) within the wave the combustion product is present in its non-equilibrium state. According to analysis of elementary routes of chemical reactions performed by Borovinskaya,38 all SHS reactions can be classied into the following ve groups.
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(5) Independent thermally coupled reactions (chemical oven): TizC?TiC WzC?WC

2.6 Chemical classes of SHS products Refractory compounds (borides, carbides, nitrides, silicides) were the rst materials synthesized by SHS. They are perfect products to be fabricated by SHS since they are characterized by high crystal lattice binding energies and their formation occurs with high heat release. To date, the range of SHS products (besides refractory compounds) includes intermetallics, complex oxides, hydrides, chalcogenides, phosphides, etc.

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Table 2 Comparative characteristics of AlN powders prepared by SHS and furnace technology and of respective sintered ceramics Impurity elements/wt % Specic surface/ m2 g21 0.60.8 2.53.5 2.05.0 3.23.5 Parameters of sintered materials Thermal conductivity/ W (m?K)21 200220 200 120170 170 10 Bending strength/ MPa 370390 207280 350 Electric break-down/ kV mm21 w20 9.6 10 w20

Method of preparation SHS SHS SHS Furnace Furnace Furnace Furnace

Grade of sample SHST SHSK SHSI AlNeL1 Ceralloy Grade F

Manufacturer ISMAN (Russia) ISMAN (Russia) ISMAN (Russia) ReaktivElektron (Russia) ART (USA) Ceradyne (GB) Tokuyama Soda (Japan)

N 31.532.5 33.733.9 33.533.8 31.032.6 33.0 33.6

O 1.21.5 0.40.7 0.50.8 0.42.9 1.0 0.9

Fe 0.10.2 0.050.08 0.060.08 0.3 v0.01 0.001

Particle size/mm v15.0 1.01.4 1.4

Task objectives in the synthesis of compounds are ensuring: (1) the highest degree of conversion, and (2) phase homogeneity of the target product. This can be achieved upon variation of the process parameters (reagents particle size, charge density, gas pressure, etc.) and also upon the addition of regulating additives whose mechanism of action can be different. The chemicals prepared by SHS under optimal conditions exhibit high quality and are a challenge to the products supplied by other manufacturers to the world market (Table 2). It should be noted that SHS technology is free of the socalled scale effect typical of other chemical processes on going from the laboratory scale to industrial-scale production, the quality of SHS products tends to increase. To date, almost any compound can be prepared by SHS upon proper variation of the charge composition and process conditions, such that the expediency of using SHS in solving this or another task is dened only by the economic factors. An important task in the synthetic chemistry of SHS is the direct synthesis of materials with a desired structure, thus avoiding preliminary preparation of powders. The greatest advance here was achieved in the synthesis of multicomponent ceramics and hard alloys (see Sections 3.2 and 3.3). Performing the SHS reaction according to the scheme BzTiB2 ? BNzTiB2 Borovinskaya et al.39 prepared the material with a quasihomogeneous structure in which the TiB2 grains were surrounded with BN playing a role of a matrix (Fig. 5a). A material of the same composition but prepared through the reaction Ti 1 2B 1 BN A BN 1 TiB2 was found to have another, skeleton-like structure in which the TiB2 grains formed bridges (Fig. 5b). The electrical resistance of the quasihomogeneous material is above 8 6 1013 Ocm (which is close to that of BN), whereas that of the skeleton-like structure is 4 6 1024 Ocm (close to that of TiB2). A reaction product formed in the matrix of an inert lling material often forms a bridged structure. Currently, the work on direct SHS production of composite materials is in progress40,41 as well as the work on time-resolved XRD of complex oxide mixtures42 and the use of large magnetic elds.43
N2

2.7 To the state of SHS products Owing to the specicity of SHS, its products may be expected to appear in their non-equilibrium (quenched) state. The state of SHS products (equilibrium or non-equlibrium) can be predicted by analyzing the ratio tsf S~ tthr where tsf and tthr are the characteristic times for structure formation in the reaction product and for thermal relaxation of sample, respectively. When S % 1, the sample cools down slowly so that the product has enough time for crystallization and, hence, appears in its equilibrium state. When S & 1, a product can be expected to appear in its non-equilibrium (quenched) state. In this case, we can talk about auto-annealing and auto-quenching, respectively. For intermediate values of S, the product structure may turn out to be rather complicated: for example, the product may have an equilibrium chemical composition but a non-equilibrium phase composition. Recently, an attempt44 was made to obtain some relevant qualitative information. For the reaction Ti 1 0.5C A TiC0.5 (off-stoichiometric carbide) the halfwidth of the main diffraction peak Dh (conventionally characterizing the state of the product equlibrium) was plotted as a function of tthr (Fig. 6). With increasing tthr, Dh is seen to decrease initially and then to

Fig. 5 The quasi-homogeneous (a) and skeleton-like (b) structure of the BN/TiB2 ceramics prepared through different reactions.

Fig. 6 Dh as a function of tthr.

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level off. This observation implies that the product is nonequilibrium for low tthr and equilibrium for high tthr. It is interesting that the saturation takes place at relatively low tthr (ca. 17 s). Interesting results concerning study of the structure formation dynamics were obtained by Rogachev et al.45 In their experiments on the quenching of combustion in burning samples, they observed the effect of recrystallization by analyzing the structure of the quenched sample at different separation distances from the combustion front. Such studies suggest the necessity of the development of the time-resolved characterization of SHS products during the SHS process, just as is being done via TRXRD.

pink corundum and appropriate moulds is being implemented at the SALYUT production association (Moscow, Russia). 3.2 Ceramic materials and items (net-shape production) Net-shape production of the nitride SHS ceramic under nitrogen pressure (up to 300 MPa) is decribed in refs. 50 and 51. As a rule, the shape and size of the combustion product replicates those of the charge blank. High applied pressure suppresses the loosening action of evolving impurity gases and decreases the porosity of the product. Some parameters of the thus-prepared BN 1 SiO2 material (Borsion) are given in Table 3. Good service parameters are exhibited (see the review in ref. 52) by the so-called black ceramic, SiN4 1 SiC 1 TiN. This material is effective for use in ball-bearings, in friction pairs, etc. 3.3 Tungsten-free hard alloys This problem claimed much attention at the initial stages of SHS research. The work was carried out in two directions:46 (1) the use of SHS-produced powders in sintering or hot pressing of hard alloys (here SHS acted as a supplier for powder metallurgy) and (2) direct SHS-production of hard alloys, omitting the preparation of powders (synthesis and structure formation in one process). In the latter case, the role of SHS is much more signicant. In the method of forced SHS compaction,5355 a still hot combustion product is subjected to mechanical densication to obtain a pore-free product.

3 Some examples of the practical implementation of SHS

3.1 SHS powders As is already known, SHS can be used to prepare crystalline, agglomerate (polycrystalline), and composite powders.46 A high hardness of some SHS products was noticed back in the 1970s. A most suitable SHS product for use as an abrasive powder was found47 to be TiC. The abrasiveness of SHSproduced powders is higher than that of the same products prepared by furnace technology. The service parameters (class of surface nish, labor productivity, service life of machined components) of the SHSproduced pastes (tested in more than 1000 machine works of Russia and the Ukraine) were found to be better than those of conventional diamond pastes. This is due to the agglomerate structure of SHS-produced TiC grains: initially, coarse agglomerate grains perform the rst ogging and then, upon their diminution, also nish up to a desired level of surface nish.48 SHS retains a strong position in the manufacturing of ceramic powders. For many years, pilot-scale production of the a-Si3N4, AlN, and BN powders has been taking place in ISMAN. The composite powder TiC 1 Cr3C2 1 Ni has found its application as a wear- and heat-resistant coating in the aircraft industry of the Ukraine. The powder of the so-called pink corundum (a solid solution of Al2O3 and Cr3O2) is obtained through the SHS reaction Cr2O3 1 CrO3 1 2Al 1 2.3C A (Al2O3Cr3O2) 1 1.3Cr3C2. Recently, pink corundum was found to be suitable for use in production moulds for the casting of heatproof alloys, in particular, turbine blades.49 In the existing technology, such moulds are being made of common corundum (a-Al2O3). The blades cast in new moulds have been found to have no burnt-on layer, which ensures a smoother blade surface (due to the higher chemical stability of pink corundum). Moreover, a more ne-grained structure of pink corundum improves the strength and service life of the blades (because of the higher thermal conductivity of pink corundum). The production of

This technique was used to prepare new hard alloys, largely for use in cutting instruments. The production of cutting inserts from STIM-5 alloys was realized on the pilot scale. The service parameters (Table 4) of these items exceeded those of existing analogs by a factor of 1.52.5. Owing to a small grain size (0.32.0 mm), a new hard alloy recently synthesized56 in the TiCNiMo system was found to exhibit high hardness (9092 HRA) and strength (1400 1600 MPa). Despite the good service parameters of STIM alloys, their mass production is restrained by the labor-consuming machining of the crude combustion product into cutting inserts. Nevertheless, these results gave impetus to the SHS production of: . items with a desired shape (or cutting inserts with a desired surface relief); . large-scale items; . functionally-graded alloys; . long-sized items (rods). An important achievement of SHS is the production largescale hard-alloy items which are impossible to prepare by

Table 3 Refractory material Borsion (BNSiO2): operation conditions and performance Destination Lining for the active zone in MHDa generators Lining for walls in plasma generators Structural material for crystal-growth facilities in the semiconductor industry Nozzles for air-plasma cutting of metals
a

Operation conditions and service parameters A ow of hot combustion products of solid metallized fuels. Temperature 3900 K, pressure 6.5 MPa Gas temperature 6000 K, pressure 0.2 MPa, concentration of electrons 1015 cm23 Temperature range 201370 uC, cyclic operation on an oxidative environment, number of temperature cycles w100

Performance Low ablation of ceramics. A 34-fold gain in withstandability Low ablation of material in the discharge zone (0.5 mm per 1800 pulses) High chemical and thermal resistance (can be used instead of quartz, graphite, and alundum ceramics) A 34-fold gain in service life

MHD ~ magnetohydrodynamic.
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Table 4 Characteristics of STIM materials Alloy grade STIM-1B/3 STIM-2 STIM-2A STIM-3B STIM-3B STIM-4 STIM-5 Composition (TiCTiB2) 1 Cu TiC 1 Ni TiC 1 (NiMo) (TiCCr3C2) 1 Ni (TiCr3C2) 1 steel TiB 1 Ti (TiCTiN) 1 (NiMo) d/g cm23 4.94 5.50 6.40 5.37 5.40 4.20 5.80 Grain size/m 57 57 12 34 24 12 12 Hardness/ HRA 93.5 90 87 92.5 92.5 86 91.5 Bending strength/MPa 700800 10001100 16001800 8001000 700800 1200 12001400 Application Cutting inserts Armor plates Instruments for punching Cutting inserts Nonscaling alloys Items resistant to thermal shock Cutting inserts

powder metallurgy. The synthesis of such items using a press facility is shown in Fig. 7. 3.4 Cast materials and items Cast materials and items are prepared by SHS involving a stage of aluminothermic reduction. Here the main task objectives are the deposition of a hard-alloy coating onto steel items and the production of ceramic-lined pipes for transportation of abrasive media. In this case, SHS is carried out in a layer of charge placed on the steel surface.57 The formed melt of solid solution penetrates into the near-surface layer of the substrate and strongly links the ceramic layer with the metal. A method for preparation of ceramic-lined pipes is based on the following classical exothermic reaction yielding melted products: MemOn 1 2/3nAl A mMe 1 1/3nAl2O3 where Me ~ Cr, Mo, W, Fe, Co, Ni. The process is carried out in a rotating tube, so that phase separation in the eld of articial gravity results in the formation of the inner Al2O3 lining. Yukhvid and Merzhanov58,59 were the rst to prepare such tubes on the laboratory scale. Odawara60 manufactured a large-scale tube (300 mm in diameter, 6 m long) for geophysical research. Sheng Yin et al. and ShuGe Zhang et al. organized the large-tonnage production (more than 10 000 tons per year) of large-scale tubes used for building pipelines (Fig. 8) in China (see also the review in ref. 61). SHS can also be used to prepare intermetallic ingots, in the recycling of metals, for sealing of defects, etc.

4 Instead of conclusions: some promising lines of further research

The most promising lines of further SHS R & D have been outlined in the collection in ref. 62 (which recently appeared in Russian) and in my lecture, SHS: Concepts of Current R & D, delivered at the VII International Symposium on SHS in Cracow (Poland).63 As mentioned above, for the preliminary analysis of SHS, of

great help are the thermodynamic calculations. To date, all of the binary systems (for which the thermodynamic functions are available) and some triple systems have already been analyzed. The signicance of thermodynamic calculations increases with an increasing number of reagents. In this context, it seems urgent to optimize the scheme of calculations in order to make them more purpose-oriented. No doubt, further efforts should be made for elucidating the mechanism of SHS reactions, in particular their zone structure and its role in the entire process. Of especial interest are the reactions that take place far behind the combustion front. Little or no attention was given to the SHS of semiconductors as well as to the synthesis of high-purity inorganic compounds. In the latter case, of interest are the SHS experiments behind a molecular shield in open space.64 Investigations on the effect of the strong external inuences on SHS provide yet another key to controlling the process. Several data on the effect of strong electric, magnetic, and electromagnetic elds give sufcient grounds for hope. What remains unclear is the effect of gravity on the mechanism of SHS reactions the numerous published data refer to the entire SHS process. Of great signicance seems to be the ionometric investigation of SHS reactions initiated by Morozov et al.65,66 Recently, Borovinskaya et al.39 initiated the studies on the regulation of product structure upon variation in the type of chemical reactions and through the structureproperties relationship. Note that the theoretical models of SHS suggested so far still do not jointly take into account the processes of combustion and structure formation, which decreases their predictive efciency. Among the advanced materials where SHS can be expected to play a positive role there are functionally graded materials, nano-sized powders, compact nano-grained materials, nonequilibrium materials (becoming equilibrium during their service life), etc. Of current interest are also gas-phase SHS (preparation of nanopowders and deposition of lms), mechano-activated SHS, SHS in centrifuges (up to 20 000 g), SHS in thin lms, etc. Many interesting aspects of SHS are related to the combustion theory, structural macrokinetics, process engineering,

Fig. 7 Press facility of ISMAN.

Fig. 8 Large-scale ceramic-lined steel pipes for transportation of abrasive media (concrete, ores, coal, etc.) SHS-produced in China.
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fundamentals of production, economic effectiveness, etc., that are beyond the scope of this article. The relevant data can be found in the cited references. The chemical, physicochemical, and structural diversity of SHS processes makes the sweeping generalization of the available data a difcult but exciting and important problem.

Acknowledgements
I am grateful to Ms M. Nasonova and Mrs I. Zakieva for preparing the art-work and page make-up, and to Dr Yu. Scheck and Dr M. Rusanova for translating the manuscript.

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