SHS of NbSi<Subscript>2</Subscript>: A Comparison Between Experiments and Simulations

Summary. Computer simulation results for the Self-propagating High-temperature Synthesis (SHS) of the intermetallic compound NbSi₂ are discussed in comparison with experiments for SHS of mechanically activated powders. The variation of wave speed of the propagation front is considered while varying Nb grain size and thermal conductivity of the starting mixture. A co-operating effect of these two parameters (due to the change in morphology of reactants after milling) is outlined.     

Crystallization and structure formation in polymer blends with strong intermodular interactions: blends of poly(ethylene oxide) and styrene-hydroxystyrene copolymers

Time-resolved synchrotron wide- and small-angle X-ray scattering experiments were used to investigate crystallization behavior and microstructure development of a nearly monodisperse poly(ethylene oxide) [PEO] (M_w = 53,500), and its melt-miscible blends with two fractionated styrene - hydroxystyrene random copolymers [SHS]. PEO crystallization rates decrease significantly in the presence of the melt-miscible SHS copolymers. All low and high molecular weight SHS blends exhibit a crystallization process at relatively short times characterized by large Avrami exponents (n), followed by a dominant process with n near that of neat PEO. A model for the crystallization of these blends is proposed.     

Regularities of self-propagating high-temperature synthesis in the solid 8-hydroxyquinoline—chloramine B system

The regularities of chemical reactions in solid 8-hydroxyquinoline—chloramine B mixtures were studied under conditions of organic self-propagating high-temperature synthesis (SHS), isothermal reaction, and thermal explosion in the 20–220 °C temperature range. Comprehensive physicochemical analysis and microstructural study of the reaction products were carried out. The temperature of SHS initiation (58 °C), the heat of the reaction (129±9 kJ mol⁻¹), the stoichiometric coefficient (1), the maximum temperature (T _max=98–140 °C), and the velocity of SHS wave propagation (u=0.15–0.55 mm s⁻¹) were determined. Depending on the ratio of the reactants (n), a low-temperature non-degeerate stable gasless mode (n≤1,T _max=115 °C,E _a=42 kcal mol⁻¹) and a high-temperature mode (n>1,T _max=140 °C,E _a=0.4 kcal mol⁻¹) are possible for SHS. The SHS affords monohydroxy and monochloro derivatives of 8-hydroxyquinoline, benzenesulfonamide, NaCl, NaOH, and H₂O. The mechanism of the solid-phase reaction at temperatures below 58 °C includes surface, solid-phase, and gas-phase diffusion; that for SHS is capillary spreading of the hydroxyquinoline melt. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2271–2284, December, 1999.     

X-ray diffraction study of self-propagating high-temperature synthesis in the Zr–Al–C system

The phase formation process in the Zr–Al–C system during self-propagating high-temperature synthesis (SHS) has been studied by time resolved X-ray diffraction (TRXRD). The “nonuniqueness” of SHS routes in ternary solid-phase systems depending on synthesis initiation conditions has been established. No formation of ternary compounds belonging to the class of MAX phases has been observed in the considered system. It has been shown that the reaction responsible for the propagation of the combustion wave is the synthesis of ZrC, if SHS is initiated by a high-temperature pulse, and the end product also incorporates intermetallide zirconium phases. At the same time, the sequential formation of the Zr[Al] solid solution, the ZrAlC _х phase, and the intermetallide ZrAl₃, ZrAl₂, and Zr₂Al₃ phases occurs in the bulk ignition of the 2Zr–Al–C mixture under the conditions of great heat withdrawal during the reaction between an Al melt and Zr particles. No initiation of the Zr–C reaction takes place due to a low enthalpy of the reactions between aluminum and zirconium.     

Preparation of a single-phase solid electrolyte La1 ? xSrxGa1 ? yMgyO3 ? (x + y)/2 by self-propagating high-temperature synthesis

Highly dispersed single-phase powders described as La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 were prepared using a method based on the principles of self-propagating high-temperature synthesis (SHS). Lanthanum, strontium, gallium, and magnesium nitrates were used in the SHS as “oxidants”, and ethylene glycol was used as the reducing agent. The initial reaction mixture was liquid. According to X-ray diffraction and scanning electron microscopy data, the sample becomes a single phase after annealing of the primary SHS product at 1200°C, which is substantially lower than in other synthetic methods. Using so active powders (grain size of about 100–130 nm), it is possible to reduce the temperature of the final annealing of the ceramics to 1275°C, which gives rise to single-phase finely dispersed ceramics having specific properties.     

Convenient, rapid synthesis of rare earth orthochromites LnCrO by self-propagating high-temperature synthesis

Lanthanide orthochromites of general formula LnCrO₃ (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Tb, Lu) and YCrO₃ have been made by self-propagating high-temperature synthesis (SHS). Four different SHS reactions were found to form LnCrO₃: reaction of Ln₂O₃, Cr and CrO₃ with NaClO₄ or Ba (ClO₄)₂ in air; reaction of Ln₂O₃, Cr and CrO₃ in oxygen; reaction of LnCl₃, CrCl₃ and NaO₂ or Na₂O₂ in air and reaction of Ln (NO₃)₃, Cr and melamine in air. Reactions were studied by DTA and TGA experiments which showed exotherms and weight losses associated with the initiation temperatures (ca. 350°C) of the SHS reactions. Maximum reaction temperature T_c and propagation velocity U_c were measured for selected reactions. X-ray powder diffraction showed a single phase orthorhombic perovskite structure was produced in all reactions. Systematic changes in the lattice parameters, cell volume and pycnometrical densities were seen as a function of lanthanide atomic number. SHS prepared LnCrO₃ samples were all shown to be weak antiferromagnets. IR spectra for the LnCrO₃ materials showed bands at 635, 480, 440, 350 and 180 cm⁻¹.     

Continuous supercritical hydrothermal synthesis: lithium secondary ion battery applications

Nanosized lithium iron phosphate (LiFePO₄) and transition metal oxide (MO, where M is Cu, Ni, Mn, Co, and Fe) particles are synthesized continuously in supercritical water at 25?C30?MPa and 400??C under various conditions for active material application in lithium secondary ion batteries. The properties of the nanoparticles, including crystallinity, particle size, surface area, and electrochemical performance, are characterized in detail. The discharge capacity of LiFePO₄ was enhanced up to 140?mAh/g using a simple carbon coating method. The LiFePO₄ particles prepared using supercritical hydrothermal synthesis (SHS) deliver the reversible and stable capacity at a current density of 0.1?C rate during ten cycles. The initial discharge capacity of the MO is in the range of 800?C1,100?mAh/g, values much higher than that of graphite. However, rapid capacity fading is observed after the first few cycles. The continuous SHS can be a promising method to produce nanosized cathode and anode materials.     

A novel method for manufacturing of aluminum foam sandwich panels

In this study, a novel method for manufacturing aluminum foam sandwich (AFS) panels via self‐propagating high temperature synthesis (SHS) has been introduced and investigated. In this method, a powder mixture of metallic aluminum and copper oxide was placed in core–sheet interface. Sandwich panel was then heated under static pressure. During heating, SHS reaction (3CuO + 2Al = Al₂O₃ + 3Cu, ΔH < 0) occurred in the interface. The generated heat from this exothermic reaction caused sheets to join the core by melting the interface and nearby. In order to evaluate the shear strength of the interface, the shear test was applied on manufactured sandwich panels, and its results were compared with those obtained from testing the sandwich panels which were produced by diffusion bonding process. Furthermore, by the aid of energy dispersive spectrometer (EDS) and X‐ray diffraction (XRD) analyses, the formation of copper in the core–sheet interface and its diffusion into the sheets and the core were investigated. In addition, by plotting the hardness values of the panels' sheets across distance, it was found that the generated heat of the exothermic reaction caused a local melting of the panel sheets and the core. These results approved that core to sheet joining in metal foam sandwich panels took place because of the SHS reaction. Significantly, this new method could be applied as a proper and alternative method for production of AFS panels. Copyright © 2010 John Wiley & Sons, Ltd.     

How "sticky" are short-range square-well fluids?

The aim of this work is to investigate to what extent the structural properties of a short-range square-well (SW) fluid of range lambda at a given packing fraction eta and reduced temperature T* = kBT/epsilon can be represented by those of a sticky-hard-sphere (SHS) fluid at the same packing fraction and an effective stickiness parameter tau(T*,lambda). Such an equivalence cannot hold for the radial distribution function g(r) since this function has a delta singularity at contact (r = sigma) in the SHS case, while it has a jump discontinuity at r = lambda sigma in the SW case. Therefore, the equivalence is explored with the cavity function y(r), i.e., we assume that [formula: see text]. Optimization of the agreement between y(SW) and y(SHS) to first order in density suggests the choice tau(T*,lambda) = [12(e(1/T* - 1)(lambda - 1)](-1). We have performed Monte Carlo (MC) simulations of the SW fluid for lambda = 1.05, 1.02, and 1.01 at several densities and temperatures T* such that tau(T*,lambda) = 0.13, 0.2, and 0.5. The resulting cavity functions have been compared with MC data of SHS fluids obtained by Miller and Frenkel[J. Phys.: Condens. Matter 16, S4901 (2004)]. Although, at given values of eta and tau, some local discrepancies between y(SW) and y(SHS) exist (especially for lambda = 1.05), the SW data converge smoothly toward the SHS values as lambda-1 decreases. In fact, precursors of the singularities of y(SHS) at certain distances due to geometrical arrangements are clearly observed in y(SW). The approximate mapping y(SW)-->y(SHS) is exploited to estimate the internal energy and structure factor of the SW fluid from those of the SHS fluid. Taking for y(SHS) the solution of the Percus-Yevick equation as well as the rational-function approximation, the radial distribution function g(r) of the SW fluid is theoretically estimated and a good agreement with our MC simulations is found. Finally, a similar study is carried out for short-range SW fluid mixtures.     

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface of H3CNO3

Global exploration of isomers and isomerization channels on the quantum chemical potential energy surface (PES) is performed for H₃CNO₃ using the Scaled Hypersphere Search‐Anharmonic Downward Distortion Following (SHS‐ADDF) method. The molecular formula of H₃CNO₃ includes functional groups of CH₃, OH, NH₂, COOH, NO, NO₂, and NO₃, which are very important in connection with amino acids and NOx. Geometrical structures and interconversion pathways are disclosed after 18719781 force calculations and 534726 Hessian calculations at the level of B3LYP/6‐31G(d). The explored results are confirmed to be valid, especially for the important lower energy regions, by re‐optimization at the higher level of B3LYP/6‐311++G(d,p). A global reaction route‐mapping using SHS‐ADDF demonstrates the entire view and undeveloped landscapes on PES of H₃CNO₃. Typical compounds of H₃CNO₃, aminoxy formic acid, hydroxycarbamic acid, aminoperformic acid, hydroxymethyl nitrite, nitromethanol, methyl nitrate, methyl peroxynitrite, and dioxaziridine, are well separated from others by very high energy‐barriers. The stable‐most conformer of H₃CNO₃ is difficult to be determined, because of seven structures existing with nearly the same energies within 5.7 kJ/mol at the level of CCSD(T)/aug‐cc‐pVTZ. © 2017 Wiley Periodicals, Inc.     

New isopropanol dehydration catalyst based on tungsten carbide prepared by modified self-propagating high-temperature synthesis

The W₂C/C catalytic system with a high specific surface area (55 m²/g) was synthesized for the first time using modified self-propagating high-temperature synthesis (SHS). The bulk and surface properties of the synthesized system were characterized using physicochemical methods and a model reaction of isopropanol conversion. It was found that the conversion of the alcohol with 100% selectivity occurs in the direction of dehydration with the formation of propylene and water. It was shown that active centers are the W(VI) surface ions of the carbide, whose activity is higher than the activity of tungsten as a constituent of the phase of WO₃.     

Carbon in boron carbide: The crystal structure of B<Subscript>11.4</Subscript>C<Subscript>3.6</Subscript>

A single crystal of boron carbide obtained from a self-propagating high-temperature synthesis (SHS) product was studied by X-ray crystallography: B_11.4C_3.6, a = 5.594(2) Å, c = 11.977(7) Å, V = 324.6(7) ų, space group R3m, Z = 3, ρ_calcd = 2.56 g/cm³, R = 0.048. The content of carbon in the single crystal was estimated at ～24 at % from analysis of the unit cell parameters, bond lengths, and the volume of B_{12 ? x} C _x icosahedra, which demonstrated the possibility of obtaining by SHS carbon-rich boron carbide crystals due to the substitution of carbon atoms for boron atoms in icosahedra. Comparison of the X-ray crystallographic data for single crystals of boron carbide with the results of quantum-chemical calculations (an ab initio method (the 3–21G basis set) with geometry optimization) showed that the C-B-C group in a crystal has a nonlinear structure.     

Quantum chemical exploration of formaldehyde clusters (H2CO)n (n = 2–4)

Global exploration of equilibrium structures and interconversion pathways on the quantum chemical potential energy surface (PES) is performed for (H₂CO)n (n = 2–4) by using the Scaled Hypersphere Search‐Anharmonic Downward Distortion Following (SHS‐ADDF) method. Density functional theoretical (DFT) calculations with empirical dispersion corrections (D3) yielded comparable results for formaldehyde dimer in comparison with recent detailed studies at CCSD(T) levels. Based on DFT‐D3 calculations, trimer and tetramer structures and their stabilities were studied. For tetramer, a highly symmetrical S₄ structure was found as the most stable form in good accordance with experimentally determined tetramer unit in the formaldehyde crystal. © 2018 Wiley Periodicals, Inc.     

自蔓延高温合成材料制备新方法

本文从自蔓延高温合成(SHS) 术语的由来、引燃技术、八种常用的自蔓延高温合成技术、自蔓延高温合成研究历史、研究现状及其发展等方面对自蔓延高温合成进行综述。     

An investigation into the self-propagating high temperature synthesis (SHS) of superconducting ceramics by thermal methods

The SHS route is based on the well-known thermite reaction, in which a strongly exothermic reaction can sustain itself and propagate in the form of a combustion wave until the reactants have been completely consumed. The successful application of the method to the synthesis of superconducting ceramics of stoichiometry RBa₂Cu₃O_y (R=Y, Er, Yb) is reported. The 123 phase was obtained when pellets of R₂O₃, BaO₂ and Cu metal in the correct proportions were dropped into a heater held at 800°C in an oxygen atmosphere and left there for only 10 minutes. Thermal methods (DSC and DTA) are excellent techniques with which to investigate the dependence of the reaction on heating rate, atmosphere and starting composition.     

Regularities governing the two-stage synthesis of cast Cr2O3/Al2O3 under conditions of the autowave synthesis

The study of the chemical, roentgen phase and structural properties of the products of combustion of system Cr₂O₃-Al-Fe₂O₃ was carried out. The analysis of the results shows the presence in the system of a set of solid solutions. The results of the study make it possible to establish the optimum regime of the heat treatment of the studied system for creating the new refractory material according to self-propagating high-temperature synthesis (SHS).     

Fundamentals, achievements, and perspectives for development of solid-flame combustion

The review is devoted to the problem of self-propagating high-temperature synthesis (SHS). The fundamentals of SHS are briefly considered, the most promising results of the experimental diagnostics and modeling of SHS processes are presented, new nonlinear phenomena and the data of thermodynamic calculations, as well as kinetic and macrokinetic studies are discussed. The main types of the SHS technology and their application for the preparation of new compounds, materials, and items along with technical and economical effectiveness are considered. New directions and perspectives of SHS are discussed. The review was prepared from materials of the author's report in the Session of the Presidium of the Russian Academy of Sciences in May, 1996. (Translated by E. Batova.) Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 8–32. January, 1997.     

SHS metallurgy of high-entropy transition metal alloys

The first positive experience in synthesis of cast high-entropy alloys in the combustion mode, referred to as SHS metallurgy (SHS is self-propagating high-temperature synthesis) has been reported. Analysis of the data obtained enables the conclusion that the one-stage SHS method is promising for the production of cast metal materials using a new principle of formation of high-entropy polymetallic alloys.     

Preparation of MB<Subscript>2</Subscript>/SiC and MB<Subscript>2</Subscript>/SiC-MC (M = Zr or Hf) powder composites which are promising materials for design of ultra-high-temperature ceramics

This survey shows the prospects of studies targeted at preparing MB₂/SiC and MB₂/SiC-MC (M = Zr or Hf) nanosized composite powders for use in the manufacture of ultra-high-temperature ceramics (UHTCs) and antioxidant protective coatings on C_f/C and C_f/SiC composites. The survey considers the specifics of various preparation methods, including sol-gel technology or precipitation followed by borothermic/ carbothermic reduction, self-propagating high-temperature synthesis (SHS), specifically variants combined with mechanochemical activation or spark plasma sintering (SPS), chemical modification of ZrB₂(HfB₂) powders with polycarbosilane followed by pyrolysis, and dispersion of appropriate ceramics with the stabilization of the slurry. The elemental and phase compositions, particle sizes, microstructures, and some other characteristics of the products reported in the related literature are summarized.     

Self-propagating high-temperature synthesis in the solid-phase triphenylphosphine-chloramine system

The macrokinetics and products of self-propagating high-temperture synthesis (SHS) in the solid-phase triphenylphosphine—chloramine system were studied by TGA-DTA, XRD, and³¹P NMR techniques. The temperature of SHS ignition (59°C), the velocity of reaction waves (1.6–5.0 mm s⁻¹), and the maximum temperature (155–239°C) in the SHS wave were measured. The chemical composition of the product obtained was established: phosphine oxide, triphenyl-N-(phenylsulfoyl)-phosphinimine, benzenesulfonamide, NaCl, and water. The scheme of chemical reactions occurring during SHS was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 301–305, February, 1999.