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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 41 (1990), S. 215-226 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Elektrochemische Untersuchungen von Na2CrO4-Na2So4-Schmelzen bei 1200 KDas elektrochemische Verhalten von Na2SO4-Na2CrO4-Lösungen an einer Arbeitselektrode aus Platin wurde mittels zyklischer Voltammetrie und durch chronopoteniometrische Messungen bei 1200°C untersucht. Dabei wurde unter kontrollierten elektrochemisch gemessenen Werten der Schmelzbasizität für basische, neutrale und saure Schmelzen gearbeitet. Trotz der thermodynamischen Stabilität von Chromitionen unter reduzierenden Bedingungen konnte keine direkte Umwandlung von Chromat in Chromit nach kathodischer Polarisation beobachtet werden. Die kathodische Reduktion von Chromat verläuft vielmehr über einen reversiblen Einelektronenladungsübergang an eine elektroaktive Zwischenform, die in einem Gleichgewicht zwischen Chromat- und Oxidionen in der Lösung entsteht.Eine irreversible chemische Reaktion verringert den Chromgehalt in der Lösung soweit, daß eine feste Substanz ausfällt, Wenn Chromat in einem aggressiven geschmolzenen Salzfilm gelost ist, ist zwar nicht zu erwarten, daß der Übergang von Chromat zu Chromit den Oxidationszustand und die Basizität stabilisiert, doch ermöglichen Chromationen eine Reduktionsreaktion, die günstiger als die Reduktion von Sulfat zu Sulfit ist; die Reduktion von Chromat führt nämlich zur Ausfällung von festem NaCrO2 bzw. Cr2O3 bzw. in basischen bzw. neutralen Lösungen. Eine starke Verschiebung der Basizitat der Schmelze kann nur im Falle von schwach sauren Lösungen mit hohem Chromatgehalt auftreten.
    Notes: The electrochemical response of Na2SO4-Na2CrO4 solutions at a Pt working electrode was established by cyclic voltammetry and chrono-potentiometry measurements at 1200 K. Experiments were made under conditions of controlled and electrochemically measured values of melt basicity for basic, neutral, and acidic melts. Despite the thermodynamic stability of chromite ions under reducing conditions, a direct conversion of chromate to chromite upon cathodic polarization was not observed. Rather, the cathodic reduction of chromate ions proceeds by a reversible one-electron charge transfer to an electroactive intermediate species formed through an equilibrium between CrO42- and oxide ions in the solution.An irreversible chemical reaction reduces the chromium solute species further to precipitate a solid. As a solute in a corrosive fused salt film, a chromate to chromite transition would not be expected to stabilize the oxidation state and basicity. However, chromate ions to provide a reduction reaction more favorable than sulfate reduction to sulfide; chromate reduction leads to the precipitation of solid NaCrO2 or Cr2O3 in basic or neutral solutions, respectively. A large shift in melt basicity can only occur for mildly acidic solutions with high chromate solute.
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  • 2
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Wachstumskinetik und Pesting-Widerstand von pulverzementationserzeugten MoSi2- und Germanium-dotierten MoSi2-DiffusionsschichtenDie rasche, zerstörende Niedrigtemperaturoxidation (Pesting) von MoSi2 ist eine entscheidende Einschränkung für die praktische Anwendung. Das Wachstum von MoSi2-Diffusionsschichten durch eine Halogenid-aktivierte Pulverzementationsmethode führt zu einem anhaftenden, oberflächlichen Salzzwischenprodukt, dessen Zusammensetzung von dem für das Wachstum der Schicht eingesetzten Halogenidaktivator abhängt. Als Folge der restlichen Salzablagerungen erfahren Schichten, die durch ein NaF-aktiviertes Pulver erzeugt wurden, nach 2500 Stunden isothermer Oxidation oder nach zyklischer Oxidation mit 600 1-Stunden-Zyklen an Luft bei 500°C keine Niedrigtemperaturoxidation. Eine zusätzliche geringfügige Verbesserung des Pesting-Widerstands wurde bei Germanium-dotierten MoSi2-Schichten beobachtet.Die Wachstumskinetik für eine dreilagige Ge-dotierte Mo(Si, Ge)2/Mo5(Si, Ge)3/Mo3(Si, Ge)-Schicht wird mit Geschwindigkeiten verglichen, die für diffusionskontrolliertes Wachstum von nicht dotierter dreilagiger Silicid- und dreilagiger Germanid-Schicht berechnet wurden. Die Aktivierungsenergie für das Diffusionswachstum von MoSi2 im festen Zustand ist die gleiche wie die für Mo(Si, Ge)2, aber die Wachstumsgeschwindigkeiten für Mo(Si, Ge)2 sind schneller. Die Aktivierungsenergie für das Diffusionswachstum im festen Zustand der inneren Mo5(Si, Ge)3- und Mo3(Si, Ge)-Schichten sind ähnlich denen von Mo5Ge3 und Mo3Ge, aber die Geschwindigkeiten sind langsamer. Die chemische Entmischung von Mo(Si, Ge)2 unter einem chemischen Potentialgradienten erzeugt ein Maximum der Ge-Konzentration an der Mo(Si, Ge)2/Mo5(Si, Ge)3-Phasengrenze, die unübliche Wachstumskinetik für die Mo5(Si, Ge)3- und Mo3(Si, Ge)-Schichten bewirkt.
    Notes: The rapid, destructive low-temperature oxidation (pesting) of MoSi2 is an important limitation to its practical use. The growth of molybdenum silicide diffusion coatings by a halide-activated pack cementation method results in an adherent superficial, salt by-product, whose composition depends on the halide activator used to grow the coating. As a consequence of the residual salt deposit, coatings grown by a NaF-activated pack did not pest after 2500 hours of isothermal oxidation or after cyclic oxidation for 600 1 hour cycles in air at 500°C. An additional minor improvement in the pesting resistance was observed for the germanium-doped MoSi2 Coatings.The growth kinetics for a three-layer Ge-doped Mo(Si, Ge)2/Mo5(Si, Ge)3/Mo3(Si, Ge) coating are compared with rates calculated for the diffusion-controlled growth of an undoped three-layer silicide and for three-layer germanide coatings. The activation energy for the solid-state diffusional growth of MoSi2 is the same as that for Mo(Si, Ge)2, but the growth rates for Mo(Si, Ge)2 are faster. The activation energies for the solid state diffusional growth of the inner Mo5(Si, Ge)3 and Mo3(Si, Ge) layers are similar to Mo5Ge3 and Mo3Ge, but the rates are slower. The chemical demixing of Mo(Si, Ge)2 under a chemical potential gradient creates a maximum in the Ge concentration at the Mo(Si, Ge)2/Mo5(Si, Ge)3 interface, which produces unusual growth kinetics for the Mo5(Si, Ge)3 and Mo3(Si, Ge) layers.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 38 (1987), S. 674-682 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Oxidation/Reduktion-Reaktionen von Molybdat-Ionen in Natriumsulfat bei 1200 KDie elektrochemischen und die damit gekoppelten chemischen Reaktionen von Molybdat-Ionen in Natriumsulfat bei 1200 K wurden mit zyklisch-voltametrischen Messungen aufgeklärt. Verschiedene Basizitäten der Schmelze wurden mit SO2-O2-Gas unterschiedlichen SO2-Gehaltes eingestellt. Die Reaktionsmechanismen wurden nach der Methode von Nicholson und Shain und mit Hilfe des Phasenstabilitäts-diagramms identifiziert.Im Stabilitätsbereich der Natriumsulfatschmelze werden Molybdat-Ionen in drei Stufen reduziert. In sauren Schmelzen ist die Reduktion von Molybdat-Ionen (Oxidationsstufe +6) zu Mo(+4) mit einer irreversiblen chemischen Reaktion gekoppelt, bei der unlösliches MoO2 gebildet wird. Molybdän-Ionen in der Oxidationsstufe (+4) werden zu Mo(+2) reduziert und sofort in einer sogenannten katalytischen. Reaktion mit oxidierenden Bestandteilen der Schmelze reoxidiert. Die Reduktion von Mo(+2) zu Mo folgt unmittelbar der vorangegangenen Reaktion in einem engen Potentialbereich und hat den gleichen katalytischen Reaktionsmechanismus. Die Reduktionsreaktionen sind reversibel. Die Oxidation von Molybdän zu Molybdat-Ionen erfolgt in drei Elektronentransfer-Stufen.
    Notes: Cyclic voltammetric studies have been used to elucidate the electrochemical and coupled chemical reactions of solute molybdate ions on sodium sulfate at 1200 K in different melt basicities fixed by SO2-O2 atmospheres. The reaction mechanism was determined by use of the Nicholson and Shain diagnostic criteria in combination with the phase stability diagram.Within the regime of sodium sulfate stability, three reduction reactions occur. In a highly acidic melt, the reduction of molybdate ions (Mo in + 6 oxidation state) to Mo as + 4 is coupled to an irreversible chemical reaction whereby molybdenum dioxide precipitates. Molybdenum in oxidation state + 4 is reduced to Mo-(+2)-species which are immediately reoxidized to Mo-(+4)-species by an oxidizing agent in the melt, a so-called catalytic reaction. The reduction of Mo-(+2)-species to molybdenum follows in a very narrow potential range close to the previous reaction and has the same catalytic reaction mechanism. The reduction reactions are reversible. The reverse oxidation of molybdenum to the molybdate ion proceeds in three electron transfer steps.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 19 (1998), S. 455-459 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Synthesis and living anionic ring-opening polymerization of 1,1-dipropylsilacyclobutane are reported. High molecular weight poly(dipropylsilylenepropylene) up to Mn = 83900 g/mol (SEC/PS standards) with low polydispersity (Mw/Mn = 1.11 to 1.22) was obtained at -20°C. End functionalization of poly-(dipropylsilylenepropylene) with chlorodimethylvinylsilane and synthesis of block copolymers with styrene was achieved. The polymers were characterized with NMR, SEC, MALDI-TOF and DSC.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemie Ingenieur Technik - CIT 67 (1995), S. 441-448 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Electromembrane Process - Part 1: Fundamentals and Mathematical Modelling. In electromembrane processes the cation or anion selectivity of polymeric ion exchange membranes can be used for various applications. Industrially important examples are membrane electrolysis and its reversal, the fuel cell or several electrodialytic processes with mono- and bipolar membranes. The electrochemical equilibrium which is responsible for membrane selectivity is discussed together with the relevant transport mechanisms within and outside the membrane. The present status and open questions of modelling electromembrane processes are considered and the efficient combination of the different phenomena into an overall model of an electrodialytic process will be addressed. Applications and a comparison of model simulations and experiments will follow as Part 2 of this survey.
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemie Ingenieur Technik - CIT 67 (1995), S. 731-739 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Electromembrane Processes, Part 2: Applications. The first part of this survey described the fundamentals and the basic equations for the mathematical modelling of electromembrane processes. In the second part a number of applications is considered. First mass transfer in ion exchange membranes is discussed. Further points are electrodialysis with bipolar membranes for the production of acid and base from a salt solution and some recent developments for the combination of electrodialysis and ion exchange.Electrodialyse with bipolar membranes allows the recycling of acids or bases from acid or base scrubbersand can also be used for electrochemical reactions in nonaqueous media. Combination of electrodialysis and ion exchange permits a continous operation of ion exchange columns with simultaneous regeneration using ion exchange membranes. This results in low consumption of regeneration chemicals and the minimisation of waste products.
    Additional Material: 17 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemie Ingenieur Technik - CIT 66 (1994), S. 1240-1240 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 8
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 689-704 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A procedure has been worked out for the column elution fractionation of polyoxypropylene glycol-toluene diisocyanate (PPG-TDI) polymers of molecular weight ∼100,000; by decreasing the column temperature from 34 to 7°C. the method was extended to degraded polymer of molecular weight ∼25,000. Graphical differentiation of the integral curves was eliminated by using Tung's empirical equations. The results for both degraded and undegraded polymer agreed with the theoretical most probable distributions; therefore, a random scission process of degradation is indicated.
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  • 10
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Further studies on the thermal degradation of POPG-TDI polymer have been carried out. It has been shown that at temperatures of ∼200°C., the predominant degradation process involves random scission of the urethane linkages to give substantial amounts of isocyanate and hydroxyl. Kinetic data suggests that the weakest links in POPG-TDI polymer are spaced at intervals of ∼10,000 in molecular weight and that they may be eliminated by pretreatment of the POPG with ethylene oxide to form a block copolyether which is used to prepare the polyurethane. At temperatures exceeding 250°C. and a greater conversion to volatile fragments (〉10%) the kinetics of degradation of POPG-TDI are similar to results for POPG and indicate scission of the polyether bonds by a combination of intramolecular proton abstraction and free radical unzipping reactions, in agreement with previous studies of POPG of much higher molecular weight.
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