Characterization of the distribution of the sintering activator boron in powder metallurgical steels with SIMS

Powder metallurgy is a well-established method for manufacturing ferrous precision parts. A very important step is sintering, which can be strongly enhanced by the formation of a liquid phase during the sintering process. Boron activates this process by forming such a liquid phase at about 1200 °C. In this work, the sintering of Fe–B was performed under the protective atmospheres of hydrogen, argon or nitrogen. Using different grain sizes of the added ferroboron leads to different formations of pores and to the formation of secondary pores. The effect of boron was investigated by means of Secondary Ion Mass Spectrometry (SIMS) supported by Scanning Electron Microscopy (SEM) and Light Microscopy (LM). To verify the influence of the process parameters on the mechanical properties, the microstructure (pore shape) was examined and impact energy measurements were performed.The concentrations of B in different samples were varied from 0.03–0.6 weight percent (wt%). Higher boron concentrations are detectable by EPMA, whereas the distributions of boron in the samples with interesting overall concentration in the low wt% range are only detectable by means of SIMS.This work shows that the distribution of boron strongly depends on its concentration and the sintering atmosphere used. At low concentration (up to 0.1 wt%) there are boride precipitations; at higher concentration there is a eutectic iron–boron grain boundary network. There is a decrease of the impact energy observed that correlates with the amount of eutectic phase.     

Formation of Carbon Filaments from 1,3-Butadiene on Fe/Al2O3 Catalysts

The formation of carbon filaments with different crystallographic and morphological characteristics in the course of 1,3-butadiene decomposition on Fe/Al₂O₃ catalysts at low (500–600°C) and high (700–800°C) temperatures was considered in terms of a carbide cycle mechanism. The conditions of formation and decomposition of an iron carbide phase in the course of formation of graphite nanotubes in the low-temperature region were studied.     

Evolution of structural features and mechanical properties during the conversion of poly[(methylamino)borazine] fibers into boron nitride fibers

Poly[(methylamino)borazine] (PolyMAB) green fibers of a mean diameter of 15 μm have been pyrolyzed under ammonia up to 1000°C and heat treated under nitrogen up to 2000°C to prepare boron nitride (BN) fibers. During the polymer-to-ceramic conversion, the mechanical properties of the green fibers increase within the 25-400°C temperature range owing to the formation of a preceramic material and remain almost constant up to 1000°C. Both the crystallinity and the mechanical properties slightly increase within the 1000-1400°C range, in association with the consolidation of the fused-B₃N₃ basal planes. A rapid increase in tensile strength (σ^R) and elastic modulus (Young's modulus E) is observed in relation with crystallization of the BN phase for fibers treated between 1400°C and 1800°C. At 2000°C, “meso-hexagonal” BN fibers of 7.5 μm in diameter are finally obtained, displaying values of σ^R=1.480 GPa and E=365 GPa. The obtention of both high mechanical properties and fine diameter for the as-prepared BN fibers is a consequence of the stretching of the green fibers on a spool which is used during their conversion into ceramic.     

Highly fluorinated graphite prepared from graphite fluoride formed using BF3 catalyst

Fluorinated graphites (CF_0.47) were obtained by reaction at room temperature of fluorine gas with graphite in the presence of boron trifluoride and hydrogen fluoride as catalysts. Their thermal treatments under fluorine at temperatures up to 600 °C lead to a progressive increase of the fluorine level resulting in an highly fluorinated graphite (CF_1.02). Whatever the fluorination level, a stage one fluorine-graphite intercalation compound is obtained. The sp² carbon hybridization is maintained for treatment temperature below 300 °C and two types of structure coexist for T_T in the range 350-550 °C. Finally, above 550 °C, carbon hybridization is sp³.The resulting materials were studied by ¹¹B, ¹H, and ¹⁹F NMR and EPR at different experimental temperatures giving informations about the intercalated fluoride species, the temperature of their removal from the host fluorocarbon matrix, as well as their mobility.     

X-ray, Raman and FTIRS studies of the microstructural evolution of zirconia particles caused by the thermal treatment

Genesis of the structure of zirconia particles prepared by precipitation of amorphous hydrated zirconia by ammonia from the ZrO(NO₃)₂ solution followed by a mild hydrothermal treatment (HTT) of precipitate, washing and calcination under air up to 1000 °C has been studied by X-ray diffraction (XRD), Raman and FTIRS. As revealed by FTIRS of lattice modes, the local structure of amorphous zirconia subjected to HTT is close to that in m-ZrO₂. This helps to obtain nearly single-phase monoclinic nanozirconia (particle size 5-15 nm) already after a mild calcination at 500 °C. Stability of this phase with nanoparticles sizes below the critical value determined by thermodynamic constraints is due to its excessive hydroxylation demonstrated by FTIRS. Dehydroxilation and sintering of these nanoparticles at higher (600-650 °C) temperatures of calcination leads to reappearance of the (111) “cubic” reflection in XRD patterns. Modeling of XRD patterns revealed that this phenomenon could be explained by polysynthetic (001) twinning earlier observed by HRTEM.     

Compacts of Boron-Doped Synthetic Diamond: Lowering of Synthesis Temperature and Its Effect on the Doping Level and Electrochemical Behavior

Substituting of metal (Co, Ni) borides for boron carbide in the boron carbide–graphite growth system for the process of diamond growth in the region of diamond thermodynamic stability allowed lowering the synthesis temperature for the electrodes of this new electrode material―boron-doped diamond compacts―significantly (by ~1000°C) without any deterioration of their electrochemical properties. On the other hand, using of amorphous boron with finer grain as compared with the boron carbide, mixed with graphite, results in a marked increase of the electrodes’ electrochemical efficiency, due to increase in their roughness after the chemical removing of boron-containing inclusions from their surfaces. Thus obtained compact electrodes have wide potential window and low background current in supporting electrolytes, they are well reproducible. Special features of their electrochemical impedance spectroscopy are similar to those of the recently studied compacts synthesized on the basis of boron carbide.     

The Relationship between the State of Active Species in a Ni/Al2O3Catalyst and the Mechanism of Growth of Filamentous Carbon

The formation of active particles and their changes in the course of 1,3-butadiene decomposition on a Ni/Al₂O₃catalyst at temperatures from 400 to 800°C were studied by high-resolution electron microscopy. It was found that carbon filaments of different types were formed at 400–800°C. The growth of thin filaments (20–30 nm in diameter) takes place at 400–600°C on a conical Ni particle located at the growing end of the filament, whereas di-symmetrical filaments 50–100 nm in diameter grow on biconical metal particles. As the carbonization temperature was increased to 700–800°C, graphite nanotubes 5–20 nm in diameter were formed. It was found that the mechanism of formation and the structure of filaments are related to the state of catalytically active species, which consist of a solid solution of carbon in the metal. It is suggested that the metastable surface nickel carbide Ni₃C_{1 – x} is an intermediate compound in the catalytic formation of graphite filaments from 1,3-butadiene. Upon termination of the reaction, the metastable Ni₃C_{1 – x} microphase is decomposed with the formation of hexagonal nickel microinclusions. The role of epitaxy in the nucleation and growth of a graphite phase on the metal is discussed. Models are presented for the growth of structurally different carbon filaments depending on the formation of active metal species at various temperatures. Considerable changes in the structure of carbon and the formation of nanotubes at 700–800°C are related to the appearance of a viscous-flow state of metal–carbon particles.     

Beitrag zum System Chrom-Kohlenstoff-Stickstoff

Zusammenfassung Das Dreistoffsystem Cr–C–N wird in zwei isothermen Schnitten bei 1100°C und 1400°C mit Hilfe von röntgenographischen Methoden untersucht. In einem Hochtemperatur-autoklaven wird der Einfluß des Stickstoffdruckes von 1–30 atm ermittelt. Die Chromcarbide lösen praktisch keinen Stickstoff, die über 1000°C nur unter Stickstoffdruck beständige Phase CrN keinen Kohlenstoff. Dagegen löst Cr₂N erhebliche Mengen an Chromcarbid. Eine ternäre Phase mit der ungefähren Zusammensetzung Cr_0,62C_0,35N_0,03 tritt bei hohem Stickstoffdruck auf. Die Gitterparameter des orthorhombischen Gitters konnten ermittelt werden.

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The ternary system Cr–C–N has been investigated by X-ray technique in isothermal sections at 1100°C and 1400°C. By means of a high temperature pressure vessel the equilibria with nitrogen up to 30 atm have been determined. The solubility of nitrogen in the chromium carbides is negligible. CrN is existent above 1000°C only under pressure of nitrogen and does not dissolve any carbon. The phase Cr₂N shows an extended range of homogeneity with respect to chromium carbide. Furthermore a ternary phase of the approximative composition Cr_0.62 C_0.35N_0.03 has been observed. This phase is existent only under nitrogen of high pressure. The lattice parameters of the orthorhombic cell have been measured.

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Mit 5 Abbildungen     

Vaporization and atomization of uranium in a graphite tube electrothermal vaporizer: a mechanistic study using electrothermal vaporization inductively coupled plasma mass spectrometry and graphite furnace atomic absorption spectrometry

The mechanism of vaporization and atomization of U in a graphite tube electrothermal vaporizer was studied using graphite furnace atomic absorption spectrometry (GFAAS) and electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). Graphite furnace AAS studies indicate U atoms are formed at temperatures above 2400°C. Using ETV-ICP-MS, an appearance temperature of 1100°C was obtained indicating that some U vaporizes as U oxide. Although U carbides form at temperatures above 2000°C, ETV-ICP-MS studies show that they do not vaporize until 2600°C. In the temperature range between 2200°C and 2600°C, U atoms in GFAAS are likely formed by thermal dissociation of U oxide, whereas at higher temperatures, U atoms are formed via thermal dissociation of U carbide.The origin of U signal suppression in ETV-ICP-MS by NaCl was also investigated. At temperatures above 2000°C, signal suppression may be caused by the accelerated rate of formation of carbide species while at temperatures below 2000°C, the presence of NaCl may cause intercalation of the U in the graphite layers resulting in partial retention of U during the vaporization step. The use of 0.3% freon-23 (CHF₃) mixed with the argon carrier gas was effective in preventing the intercalation of U in graphite and U carbide formation at 2700°C.     

Phase transformation of boron nitride under hypothermal conditions

Phase transformation among different boron nitride (BN) phases in hydrothermal solution was investigated. It was found that hexagonal boron nitride (hBN) firstly formed in the solution at relatively low temperature (i.e., 220 °C). After that, a spot of hBN began to transform into wurtzite boron nitride (wBN) and cubic boron nitride (cBN) at 230 °C. More and more hBN converted into wBN and cBN with the increase in temperature, and this transformation process completed at 300 °C. In this paper, we have explained the mechanism of the above phase transformation by using a reported “puckering mechanism”.     

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO₂ monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.     

A review of heat treatment on polyacrylonitrile fiber

Developing carbon fiber from polyacrylonitrile (PAN) based fiber is generally subjected to three processes namely stabilization, carbonization, and graphitization under controlled conditions. The PAN fiber is first stretched and simultaneously oxidized in a temperature range of 200-300 °C. This treatment converts thermoplastic PAN to a non-plastic cyclic or a ladder compound. After oxidation, the fibers are carbonized at about 1000 °C in inert atmosphere which is usually nitrogen. Then, in order to improve the ordering and orientation of the crystallites in the direction of the fiber axis, the fiber must be heated at about 1500-3000 °C until the polymer contains 92-100%. High temperature process generally leads to higher modulus fibers which expel impurities in the chain as volatile by-products. During heating treatment, the fiber shrinks in diameter, builds the structure into a large structure and upgrades the strength by removing the initial nitrogen content of PAN precursor and the timing of nitrogen. With better-controlled condition, the strength of the fiber can achieve up to 400 GPa after this pyrolysis process.     

The effects of annealing in inert atmospheres and of oxygen concentration on chemiluminescence from polypropylene

It has been shown that heating polypropylene powder under a nitrogen atmosphere leads to the significant prolongation of the oxidation induction time measured by chemiluminescence in oxygen at 130 and 140 °C. While heating in nitrogen from 0 to 4 h at 140 °C leads to the linear increase of oxidation induction time, the maximum chemiluminescence intensity I_stat increases with the time of sample annealing until 2 h; then it starts to decay. The different and sometime unknown thermal history of the sample may thus explain the scatter of induction times of oxidation observed with different PPs whether they be pure or stabilised. Maximum chemiluminescence intensity plotted vs. concentration of oxygen in the surrounding atmosphere at 130 and 140 °C also increases linearly; however, this does not correspond with very small reduction of oxidation induction time. The four-parametric “master equations” used in our earlier papers were applied to fit the chemiluminescence runs both in oxygen and in nitrogen. The equation operates with the rate constants of hydroperoxide decomposition and oxidation spreading but at the same time, it takes into account the possible effect of oxidation products on decomposition of hydroperoxides.     

Comparison of sample preparation methods for determination of free carbon in boron carbide by X-ray powder diffraction

Several sample preparation methods were evaluated for determination of free carbon in boron carbide powders by quantitative X-ray diffraction method, including ultrasonication, wet ball milling and dry ball milling–wet mixing. Quantitation was based on measuring the integral peak area ratio of the diffraction lines of graphite (002) to boron carbide (012) in samples spiked with pure graphite. The dry milling–wet mixing method provided the best precision and accuracy in all the measurements as well as in determination of free carbon in a boron carbide reference material. There was a linear relationship between the integral peak area ratios and graphite added to boron carbide samples which were purified from their free carbon content. The method provided a low detection limit of 0.05 wt% free carbon.     

Vacuum fusion determination of oxygen in gadolinium,terbium metal and iron-terbium alloy

The extraction conditions for the accurate determination of oxygen in gadolinium, terbium and iron-terbium alloy using vacuum fusion analysis were studied. The influence of the gettering effect, the analyzing temperature and the weight ratio of the bath metal to the sample were investigated. Oxygen values of gadolinium and terbium were measured by the graphite crucible, the graphite capsule, the tin bath, the iron-tin bath and the platinum-tin bath techniques in the temperature range of 1500–2100 °C using vacuum fusion analysis. These oxygen values were compared with those obtained by inert gas fusion analysis. In inert gas fusion analysis, the samples were analyzed with iron and tin in a tin capsule, and the samples with platinum in a tin capsule were analyzed in a graphite capsule enclosing with carbon powder. Oxygen values of both metal samples in the graphite capsule at 2000 °C, with an iron-tin bath at 1850 °C and a platinum-tin bath at 2000 °C in vacuum fusion analysis, were respectively in good agreement within their errors; the oxygen values of gadolinium were also in good agreement with that from inert gas fusion analysis in the iron-tin bath, but those of terbium were not in agreement. This agreement for gadolinium guarantees the reliability of the conditions for the accurate determination, and the difference of oxygen values for terbium suggests a need for further consideration on the conditions of the inert gas fusion analysis.     

Effect of nitrogen-doping temperature on the structure and photocatalytic activity of the B,N-doped TiO2

B,N-TiO₂ photocatalysts were synthesized by boron doping firstly and subsequently nitrogen doping in NH₃ at variable temperatures. The effects of the nitrogen doping temperature on the structure and photocatalytic activity of the B,N-codoped TiO₂ were investigated. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis diffuse reflectance spectrum (DRS), electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity was evaluated with photocatalytic degradation of methyl orange dye (MO) under visible light and UV-visible light irradiation. The results suggested that the boron and nitrogen can be incorporated into the TiO₂ lattice either interstitially or substitutionally or both, while the Ti-O-B-N structure plays a vital role in photocatalytic activity in visible light region. The optimal nitrogen doping temperature is 550 °C. Higher temperature may form many oxygen vacancies and Ti³⁺ species, resulting in the decrease of photocatalytic activity in visible light.     

High-temperature reactions in systems of interest for spectrochemical analysis

Summary Reactions taking place in the systems graphite—boron carbide—a third component in the controlled temperature range of 1000–2000° C have been investigated by the spectrochemical and X-ray diffraction methods. It has been found that boron evaporates at 1200° C when NaF or LiF were added, at 1600° C when ZnF₂ was added and at 1900° C when CaF₂ was added as a third component.In the boron carbide-graphite-magnesium oxide system, magnesium borate, Mg₃(BO₃)₂, was found to be formed at high temperatures. A new phase, aluminium borate, 9 Al₂O₃·2 B₂O₃, was also found with addition of aluminium trioxide as the third component. Vanadium pentoxide added forms vanadium boride, VB₂. In the graphite—boron carbide—silicon dioxide system several phases are found but not identified. With calcium fluoride as the third component no changes occured up to 1900° C, while at 2000° C there is a hardly visible formation of calcium hexaboride. In the case of sodium fluoride new phases are sometimes found, but not identified.

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Hochtemperaturreaktionen in spektralanalytisch wichtigen Systemen1. Reaktionen in den Systemen von Graphit und Borcarbid mit einer dritten Komponente

Zusammenfassung Die Reaktionen wurden im Bereich von 1000–2000° C durch Spektralanalyse und Röntgendiffraktometrie untersucht. Dabei wurde gefunden, daß Bor bei 1200° C verdampft, wenn NaF oder LiF zugesetzt werden, bei 1600° C bei Zugabe von ZnF₂ und bei 1900° C bei Zusatz von CaF₂. Im System Borcarbid-Graphit-MgO wurde bei hohen Temperaturen Mg₃(B0₃)₂ gebildet. Bei Gemischen mit Al₂O₃ wurde 9 Al₂O₃·2 B₂O₃ gefunden. Bei Zusatz von V₂O₅ wurde VB₂ gebildet. Mehrere Phasen, die aber nicht identifiziert wurden, konnten im System Graphit—Borcarbid—SiO₂ gefunden werden. Mit CaF₂ wurden bis 1900° C keine Veränderungen beobachtet, während bei 2000° C CaB₆ in geringen Mengen auftritt. Im Falle von NaF treten gelegentlich neue Phasen auf, die jedoch nicht identifiziert wurden.

     

Bestimmung von Cadmium durch flammenlose Atom-Absorptions-Spektralphotometrie

Zusammenfassung Der Einfluß der Carbidbeschichtung von Graphitrohren auf die Bestimmung von Cd mit der flammenlosen AAS wurde systematisch untersucht. Dazu wurden die Graphitrohröfen mit Zr-, Nb-, Ta-, Mo- und W-Salzlösungen imprägniert, getrocknet und anschließend zur Einleitung der Carbidbildung bei 2600° C geglüht. Es zeigte sich, daß die Oberflächenbehandlung mit Carbidbildnern insgesamt die Lebensdauer des Graphitrohres in Anwesenheit starker Oxidationsmittel erhöht. Außerdem ließen sich höhere Matrix-Zersetzungstemperaturen ohne Cadmium-Verluste erreichen. Die Beschichtung mit Nb-, Ta- und W-Carbid erbrachte auch eine erhöhte Reproduzierbarkeit. Die günstigsten Ergebnisse lieferte die Ta-Beschichtung mit einer Zersetzungstemperatur von 450° C bei Verwendung von N₂-Schutzgas, die bei Anwendung starker Oxidationsmittel auf 600° C gesteigert werden konnte. Damit erlaubt die TaBeschichtung die direkte Cd-Bestimmung selbst in Gegenwart geringer organischer Matrixanteile. Gleichzeitig waren Reproduzierbarkeit und Empfindlichkeit gegenüber dem unbeschichteten Rohr deutlich verbessert.

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Determination of cadmium by flameless atomic-absorption spectroscopy

Summary The influence of coating of graphite furnace tubes with carbide forming metals on the determination of Cd by flameless AAS has been investigated systematically. The graphite furnace tubes have been impregnated with Zr, Nb, Ta, Mo or W salt solutions, dried and subsequently annealed up to 2,600° C to initiate carbide formation. It has been found that the surface treatment with carbide forming metals increased the lifetime of the graphite tube in the presence of strongly oxidizing agents. Furthermore, higher decomposition temperatures could be applied without Cd losses and coating with Nb. Ta and W carbide led to higher reproducibility. Best results have been obtained by coating with Ta allowing a decomposition temperature of about 450° C for N₂ as inert gas, that could even be enhanced to 600° C by application of strongly oxidizing agents. Thereby Ta coating makes possible direct Cd determination even in the presence of small organic admixtures to the matrix. At the same time reproducibility and sensitivity were improved as against the uncoated tube.

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Herrn Prof. Dr. H. Weisz zum 60. Geburtstag gewidmet     

Nitrogen uptake of nickel free austenitic stainless steel powder during heat treatment—an XPS study

In austenitic stainless steel nitrogen stabilizes the austenitic phase, improves the mechanical properties and increases the corrosion resistance. Nitrogen alloying enables to produce austenitic steels without the element nickel which is high priced and classified as allergy inducing. A novel production route is nitrogen alloying of CrMn‐prealloyed steel powder via the gas phase. This is beneficial as the nitrogen content can be adjusted above the amount that is reached during conventional casting. A problem which has to be overcome is the oxide layer present on the powder surface which impedes both the sintering process and the uptake of nitrogen. This study focuses on whether heat treatment under pure nitrogen is an appropriate procedure to enable sintering and nitrogen uptake by reduction of surface oxides. X‐ray photoelectron spectroscopy (XPS) in combination with scanning electron microscopy (SEM) and energy dispersive X‐ray spectrometry (EDS) are used to investigate the surface of powdered FeMn19Cr17C0.4N heat treated under nitrogen atmosphere. The analyses showed reduction of iron oxides already at 500 °C leading to oxide‐free metallic surface zones. Mn and Cr oxides are reduced at higher temperatures. Distinct nitrogen uptake was registered, and successful subsequent sintering was reached. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface-fluorinated graphite anode materials for Li-ion batteries

Surface modification of graphite powder has been performed by chemical fluorination using elemental fluorine at 200 °C and 300 °C. This process leads to an increase of the BET surface area due to partial CC bond breaking. Surface analyses performed by secondary ions mass spectrometry have shown that the H + O content at the surface of graphite is significantly decreased by this fluorination treatment. Fluorinated graphite powders have been tested as negative electrodes in Li-ion battery, chronopotentiometry measurements have shown that the fluorinated graphite exhibits better electrochemical performances than raw graphite powder notably due to an increase of the surface area which allows the storage of a higher amount of lithium into the host lattice. In addition, impedance measurements performed in a delithiated state have shown a significant decrease of the total cell resistance, i.e. a decrease of both the charge transfer resistance and the resistance related to the solid electrolyte interface (SEI) layer.