Crystal Chemistry of Complex Carbides and Related Compounds

Numerous metal carbides can be discussed in a rather uniform way by means of structural features, mainly characterized by the mode of linking of octahedral and occasionally trigonal prismatic [M₆C] groups (M = transition element). From this point of view perovskite carbides (M₃M′C, M′ = another transition or A-group element) and derivatives, β-Mn carbides (M₃M′₂C), κ-carbides, carbides with V₃AsC- and Cr₂AlC type structures and derivatives, η-carbides (M₃M′₃C) and carbides having the filled Mn₅Si₃ type structure will be treated. The high stability of these complex carbides is due to the strong bonding M? C and additional bonding of M? M′ atoms forming an ordered parent lattice. Besides the interstitial principle of filling of lattice holes (by isolated carbon atoms), substitution with A-group elements may also take place. Thus in borocarbides extended structural elements occur.     

New complex transition metal carbides formed on an electron microscope heating stage

Particles shown to be complex carbides of copper. nickel, molybdenum.tungsten. gold, silver and titanium along with carbides of the elements in stainless steel, were formed on an electron microscope heating stage. These particles were observed to form on thin carbon films coating the electron microscope grids of the metals listed above. The d-spacings measured for these particles are essentially the same as those that are observed with a mixture of the complex carbides of general formula M₆C and M₂₃C₆. Electron microprobe analysis was performed on the particles formed in the microscope. and the analysis confirmed the presence of the respective metals within the particles. In general, the various metal carbides were observed to form at different temperatures on different metal grids.     

Structural chemistry of complex carbides and related compounds

Complex carbides formed in ternary systems of a transition element (M), a B-group element (M′), and carbon and having a formula M₂M′C (H-phase) or M₃M′C (perovskite carbide) occur frequently. This reflects the simple geometry of the atomic arrangement of the metals and the filling mode by an interstitial stabilizer such as carbon or nitrogen. The phase relationship of the ternary combinations {Ti, Zr, Hf, V, Nb, Ta, Cr, Mn, and Ni}-aluminum-carbon was investigated. New complex carbides were found with the corresponding zirconium, hafnium, and tantalum combinations. The crystal structures in the case of Zr- and Hf-containing complex carbides can be characterized by a twelve-metal-layer sequence and by a ten-metal-layer sequence with carbon atoms again filling octahedral voids. The transition of structure types from TiC, Ti₂AlC, Ti₃SiC₂, ZrAlC₂, Zr₂Al₃C₅, to Al₄C₃ is also discussed.     

Mössbauer effect study of carbides and silico-carbides. II. (Mn1−xFex)5SiC

The substitution of iron in Mn₅SiC has been studied by Mössbauer spectroscopy at room temperature. The Mn₃ site is the first saturated site while the filling of the Mn₄ site is the most difficult. The magnitude of the quadrupole splittings of iron atoms having two carbon nearest neighbors at a distance close to 2 Å in Fe₃C, Fe₅C₂, Mn₅SiC, and some M₃M′C perovskite carbides in the paramagnetic state are discussed. These quadrupole splittings are practically insensitive to the metallic neighborhood of the sites under consideration. They increase regularly with the angle of the two iron-carbon bonds.     

Compositional and structural characterization of alloyed carbide by 3D atom probe and high‐resolution TEM

During tempering of solute supersaturated ferrous martensite, the face‐centered cubic MC‐type carbides (M is alloy elements) such as VC and NbC phases usually co‐precipitate on crystal defects such as dislocation and take on plate‐like morphology. Over‐tempering makes the plate‐like shape change to spherical shape because of Ostwald coarsening. The coarsening process strongly correlates to the diffusion behaviors of the carbon and carbide‐forming elements, and consequently inhomogeneous compositional and structural distribution in the carbides is formed. Three‐dimensional atom probe and high‐resolution transmission electron microscopy have been proved useful methods to characterize the composition, morphology and nanostructure of the carbides that precipitate in a quench‐tempered micro‐alloyed steel. Depending on the actual affinity with C and the diffusion behavior, Si and Al are rejected from the alloy carbide, whereas Mn, V and Nb are inhomogeneously enriched in it. The morphology and structure change with the compositional redistribution. During the coarsening process of the pre‐existing plate‐like carbide, transition carbide that is semi‐coherent with ferritic matrix is formed because of the disparity in diffusion ratio of different solutes. A core–shell complex nanostructure is consequently formed in the coarsening carbide, and the core and shell are identified as V₈C₇ enriched in Mn, Mo and Mo₂C, respectively. Copyright © 2013 John Wiley & Sons, Ltd.     

Phenolic resin as a carbon source for the synthesis of monometallic Mo and bimetallic CoMo carbides via carbothermal reduction route

It was the first time that phenolic resin (PR) was used as a carbon source for the synthesis of nanostructured monometallic Mo and bimetallic CoMo carbides via carbothermal reduction route. The results showed that phase-pure β-Mo₂C can be formed under an Ar atmosphere at 900°C or a H₂ atmosphere above 700°C. However, almost pure CoMo carbides (Co₃Mo₃C and Co₆Mo₆C) can be obtained only under a H₂ atmosphere at a low temperature of 630°C for 24 and 48 h, respectively. The role of PR in the preparation process has been investigated and a detailed formation mechanism was proposed based on the experimental results.     

Transmission electron microscope and scanning auger investigations of temper-embrittled 12% Cr steel

Summary Reversible temper-embrittlement of 12% Cr martensitic steel was investigated. It was observed by SEM that morphology of the carbides found on the smooth intercrystalline fracture facets of the embrittled sample is much different from M₂₃C₆ carbides observed by TEM on the former austenite grain boundaries. Morphology of the carbides on the smooth facets matches TEM data for the M₇C₃ carbides formed during the embrittlement treatment in some distance from the former austenite grain boundaries. Associated SAM analysis data suggest that phosphorus tends to concentrate within stress fields formed around M₇C₃ carbides.

---

Untersuchungen von Versprödungseffekten in Cr-Iegierten Stählen mit Transmissionelektronenmikroskopie und Auger-Spektroskopie

     

Note on thermodynamic instability ofM 4C3-type carbides of gallium group metals

The paper deals with thermodynamic stability of hypothetical solid binaryM ₄C₃ carbides of gallium, indium and thallium. Heats of formation whose contribution to the stability of these compounds is dominant, were estimated by two independent methods: semiempirical theory ofMiedema and empirical trends in the heats of formation of nitrides and carbides of Group III elements. Entropies were calculated with the use of theCantor equation. The estimated values suggest thatM ₄C₃ carbides of gallium, indium and thallium are thermodynamically unstable with regard to their decomposition to elements.

---

Über die Instabilität von Galliumgruppenkarbiden des TypsM ₄C₃

Zusammenfassung Es wird die thermodynamische Stabilität von hypothetischen Gallium-, Indium- und Thalliumkarbiden diskutiert. Zur Abschätzung von Bildungswärmen, deren Beitrag zur Stabilität dieser Verbindungen dominant ist, wurden zwei unabhängige Methoden verwendet: die semiempirischeMiedema-Theorie und empirische Trends der Bildungswärmen bei den Nitriden und Karbiden der Elemente der III. Gruppe. Die Entropiewerte wurden mittels derCantor-Gleichung berechnet. Aus den abgeschätzten Werten geht hervor, daß die Galliumgruppenkarbide bezüglich der Zersetzung in die Elemente thermodynamisch instabil sind.

     

Dosage de l'oxygene dans l'uranium et ses composes par la methode au monochlorure de soufre

A sulfur monochloride method is proposed for the determination of oxygen in uranium compounds. Sulfur monochloride reacts with oxygenated compounds at temperatures depending upon their nature; the sulfur dioxide produced is titrated by iodometry, after the excess reagent has been eliminated by a selective adsorption-desorption process using activated charcoal. This method has been successfully applied to uranium oxides (UO₂, U₃O₈), to mixtures of uranium dioxide with uranium, uranium nitride, and uranium carbide, and to substituted carbides (UC_1-xO_x). The results are generally satisfactory for oxygen contents higher than 500 p.p.m. However, in the presence of free or combined carbon, this limit is considerably higher. A loss of oxygen as carbon monoxide is also possible, and a simultaneous determination of carbon monoxide must be carried out. The relative error is of the order of a few per cent.     

Diffusion of Organic Vapors in Materials for Gas Sensing Application

Mass-variation measurements were carried out on carbon black (CB)-poly(vinyl chloride) (PVC) composite film with 40% by weight of di(2-ethylhexyl)-phthalate (DOP), cast on resonant piezo-layer (RPL) elements of lead zirconat titanate (PZT). Even if anomalous diffusion is predicted by fitting the data with M_t/M_∞=kt^α, the fractional uptake M_t/M_∞ is linear with the square root of the time up to M_t/M_∞=0.6, suggesting Fickian behavour. The anomalous values of α are probably due to experimental time lag. A dependence of the diffusion on the morphology of the material and the penetrant shape and flexibility has been found.     

SEM and EDXS analysis of the reaction products of compounds AxM6X8 (A = Tl,K; M = V,Ti; X = S,Se) with I2/CH3CN and H2O

The ternary transition metal chalcogenides A_xM₆X₈ (A=Tl, K; M=V, Ti; X=S, Se) build up a three dimensional framework with large hexagonal channels running parallel to the crystallographic c-axis. The electropositive elements thallium or potassium are confined within these channels. It is possible to remove the Tl or K atoms via a chemical redox reaction with an I₂/CH₃CN solution or with H₂O. Using SEM it is demonstrated that the host matrix “V₆S₈” is only slightly affected by the redox agent. In contrast the host matrix “Ti₆Se₈” of Tl_xTi₆Se₈ reacts with the I₂/CH₃CN solution. The results of the EDXS analyses clearly show that the removal of the electropositive elements proceeds only along the large channels and not through the host matrix.     

Kinetics of the oxidation of nitric oxide by chlorine and oxygen in nonaqueous media

The kinetics of the reaction between nitric oxide and chlorine have been investigated in both carbon tetrachloride and glacial acetic acid. The nitric oxide-oxygen reaction has been investigated in carbon tetrachloride. The appearance of product, NOCl or NO₂, was monitored spectrophotometrically at a wavelength of 475 nm for NOCl and 343 nm for NO₂. These measurements were performed using an Amino-Morrow stopped-flow apparatus equipped with a Beckman D U monochromator. The data for both the NO? Cl₂ and NO? O₂ systems could be fitted to the third-order integrated equation and the calculated rate constants were 2.75 × 10³ M^?2 s^?1 and 2.79 × 10⁶ M² s^?1, respectively, at 25.1°C. There was a noted increase in rate constants on changing the solvent from carbon tetrachloride to acetic acid. The likelihood of a termolecular encounter is inherent in the mechanism, however, no real evidence to substantiate either a direct termolecular or a series of two bimolecular steps has been obtained, although a ?7 kcal for ΔH⁰ would support the latter.     

Solid-phase synthesis of boron carbides ReB2C (Re = Ho,Tm, Lu) of rare earth elements

Approaches to solid-phase synthesis of boron carbides of heavy rare-earth elements using the hydride phase have been considered. Synthetic procedures with the use of carbon in the forms of carbon black and pyrographite were tested under atmospheric pressure, in medium and high vacuum. The obtained samples were characterized by X-ray and chemical (elemental) analyzes. A technique for obtaining compact samples of boron carbides of Ho, Tm, and Lu, which are homogeneous in the phase composition, has been developed.

     

Development and application of high strength ternary boride base cermets

Reaction boronizing sintering is a novel strategy to form a ternary boride coexisting with a metal matrix in a cermet during liquid phase sintering. This new sintering technique has successfully developed world first ternary boride base cermets with excellent mechanical properties such as Mo₂FeB₂, Mo₂NiB₂ and WCoB base ones.In these cermets Mo₂FeB₂ and Mo₂NiB₂ base ones consist of a tetragonal M₃B₂ (M: metal)-type complex boride as a hard phase and a transition metal base matrix. The cermets have already been applied to wear resistant applications such as injection molding machine parts, can making tools, and hot copper extruding dies, etc.This paper focuses on the characteristics, effects of the additional elements on the mechanical properties and structure, and practical applications of the ternary boride base cermets.     

Cathodic voltammetric determination of gold

Cathodic voltammetry at a carbon paste electrode has been evaluated as a technique for the analysis of gold. In the absence of interfering elements the technique is suitable for determinations at concentrations down to 10^?6M. Differentiation of the reduction peak current increases the sensitivity, permitting the determination of gold at concentrations of 10^?7M.     

Calculations of Jahn-Teller coupling constants in the weak-field basis via the angular overlap model: a simple operator equivalent technique

Within the framework of the angular overlap model the matrix elements of the linear Jahn-Teller operator may easily be calculated in the weak-field basis in terms of simple operator equivalents. The method is applied to the calculation of the 〈M_J|?V/?Q|M_j〉 matrix elements for the |LSJMj〉 ground states of t^x species (x = 1) ? 13) in )^* symmetry.     

Quantitation of major elements with secondary ion mass spectrometry by using M 2 + -molecular ions

A new quantitation method, based on the detection of M ₂ ⁺ molecular ions, is presented. It has been shown that M ₂ ⁺ molecular ions are formed by a recombination process between independently sputtered M and M⁺ particles. Based on this formation mechanism, it will be demonstrated that M ₂ ⁺ molecular ions can be used to quantitate major elements. The method will be used for quantitation of an Al _x Ga_1?x As multilayer. Furthermore, it will be shown that some matrix effects can be explained by the energy dependence of instrument transmission.     

Thermogravimetric study of the carburization and coking of unsupported and carbon-supported Fe,Mo and Fe−Mo catalysts for fischer-tropsch synthesis

Carburization and coke deposition of unsupported and carbon-supported Fe, Mo and Fe?Mo catalysts in syngas have been studied using thermogravimetry. Compositions of the carbides formed are evaluated on the basis of the amount of metals in the catalysts and amount of carbon deposited during carburization. It is shown that carburization temperature and the nature of the carbides formed (Fe₅C₂ and Fe₂C for iron and Mo₂C for molybdenum) depend on the metals but are influenced by the support and metal loading. Coke deposition on these catalysts takes place as soon as carburization is complete.     

Mass-spectrometric study of the sesquiterpene lactone grossmisin and its derivatives

Summary The dissociative ionization of grossmisin [O–D]grossmisin, and two of its derivatives have been studied. The appearance of the main fragments in the mass spectrum of grossmisin is due to the elimination by the M⁺ ion of H₂O and CO molecules and CH₃ and OH radicals in various sequences. The hypothesis has been put forward that in the splitting off of a CH₃COOH molecule by the M^+° ion of acetylgrossmisin a rearrangement of the lactone ring takes place with its reclosure at the C₆ carbon atom of the seven-membered ring.M. V. Lomonosov Moscow State University. Patrice Lumumba International Friendship University, Moscow. All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 344–349, May–June, 1977.     

Error matrices in gas-electron diffraction: II. Influence of weight matrix

The properties of three different forms of error matrices in electron diffraction are investigated, assuming the presence of stationary, Gaussian, Markovian noise in the primary data. The error matrices studied are M_x^p based on the optimum weight matrix P the bona fide error matrix M_x^w based on the nonoptimum weight matrix W, and the false error matrix M_x^o commonly calculated by diffractionists using the formula for the optimum error matrix while incorporating a nonoptimum weighting. Simple formulae relating the elements of the various matrices are derived in the case where W is the best diagonal weight matrix and where geometric constraints are not imposed on parameters. The influence of geometric constraints is tested. Calculations indicate that diagonal weight matrices in ordinary circumstances give results imperceptibly inferior to the results obtained with the best nondiagonal weight matrices. Elements of M_x^w closely approach those of M_x^p whereas elements of the false error matrix, taken alone, may be very misleading.