Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.     

Energetic 2,2‐Dimethyltriazanium Salts: A New Family of Nitrogen‐Rich Hydrazine Derivatives

Amination of 1,1‐dimethylhydrazine with NH₂Cl or hydroxylamine‐O‐sulfonic acid yields 2,2‐dimethyltriazanium (DMTZ) chloride ( 3 ) and sulphate ( 4 ), respectively. The DMTZ cation was paired with the nitrogen‐rich anions 5‐aminotetrazolate ( 5 ), 5‐nitrotetrazolate ( 6 ), 5,5′‐azobistetrazolate ( 7 ), and azide ( 8 ), yielding a new family of energetic salts. The synthesis was carried out by metathesis reactions of salts 3 or 4 and a suitable silver or barium salt. To minimize the risks involved when using heavy metal salts, we used electrodialysis for the synthesis of azide 8 , which avoids the use of highly sensitive species. The DMTZ derivatives were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, and X‐ray diffraction. Thermal stabilities were measured using DSC analysis and their sensitivities towards classical stimuli were determined using standard tests. Lastly, the relationship between hydrogen bonding in the solid state and sensitivity is discussed.     

A Ruthenium(II)–Copper(II) Dyad for the Photocatalytic Oxygenation of Organic Substrates Mediated by Dioxygen Activation

Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of a catalytic system requires regeneration of the Cu^I active redox state from Cu^II. This is usually achieved using extra reducers that can compete with the Cu^II(O₂) oxidizing species, causing a loss of efficiency. An alternative would consist of using a photosensitizer to control the reduction process. Association of a Ru^II photosensitizing subunit with a Cu^II pre‐catalytic moiety assembled within a unique entity is shown to fulfill these requirements. In presence of a sacrificial electron donor and light, electron transfer occurs from the Ru^II center to Cu^II. In presence of dioxygen, this dyad proved to be efficient for sulfide, phosphine, and alkene catalytic oxygenation. Mechanistic investigations gave evidence about a predominant ³O₂ activation pathway by the Cu^I moiety.     

Rheologische Eigenschaften konzentrierter Polyisobutylenlösungen in Lösungsmitteln verschiedener thermodynamischer Güte

Zusammenfassung Die Konzentrationsabhängigkeit der viskoelastischen Eigenschaften von Polyisobutylenlösungen in Lösungsmitteln mit verschiedener thermodynamischer Güte wurde mit einem Weissenberg-Rheogoniometer untersucht. Es wurde festgestellt, daß die Spriggssche 4-Parameter-Theorie den Übergang von niedrigen zu hohen Schergeschwindigkeiten nicht zufriedenstellend beschreibt. Die Schergeschwindigkeitsabhängigkeit des Schermoduls zeigt in den verschiedenen Lösungsmitteln ein Maximum. Die Konzentrationsabhängigkeit des Maximums wird durch das Molekulargewicht des Polymeren und die Lösungsmittelgüte wenig beeinflußt. Die Schergeschwindigkeiten, die dem Maximum entsprechen, zeigen dagegen eine Konzentrationsabhängigkeit, die von der Lösungsmittelgüte abhängt. Die Konzentrationsabhängigkeit und der Einfluß der Lösungsmittelgüte bei niedriger Scherrate entsprechen nur qualitativ den Voraussagen der strukturrheologischen Theorien.

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Summary Concentration dependence of viscoelastic properties of polyisobutylene solutions in thermodynamically different solvents was investigated in the Weissenberg-Rheogoniometer. It was found, that the 4-Parameter Spriggs theory does not exactly describe the changes of rheological properties of these solutions by changing the shear rate from low to high.The shear modulus as a function of the shear rate has a maximum for the investigated solutions. The concentration dependence of this maximum shows a low sensitivity for the molecular weight of the polymer as well as for the thermodynamical properties of the solvent. The shear rate corresponding to the maximum value of the shear modulus is dependent on the concentration and the thermodynamical properties of the solvent. The existing structural rheological theories describe only qualitatively the concentration dependence and the influence of the solvent on the structural parameters even at low shear rates.

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Mit 11 Abbildungen und 4 Tabellen     

From Lignin‐derived Aromatic Compounds to Novel Biobased Polymers

Nowadays, the synthesis of (semi)aromatic polymers from lignin derivatives is of major interest, as aromatic compounds are key intermediates in the manufacture of polymers and lignin is the main source of aromatic biobased substrates. Phenols with a variety of chemical structures can be obtained from lignin deconstruction; among them, vanillin and ferulic acid are the main ones. Depending on the phenol substrates, different chemical modifications and polymerization pathways are developed, leading to (semi)aromatic polymers covering a wide range of thermomechanical properties. This review discusses the synthesis and properties of thermosets (vinyl ester resins, cyanate ester, epoxy, and benzoxazine resins) and thermoplastic polymers (polyesters, polyanhydrides, Schiff base polymers, polyacetals, polyoxalates, polycarbonates, acrylate polymers) prepared from vanillin, ferulic acid, guaiacol, syringaldehyde, or 4‐hydroxybenzoic acid.

     

Generalizations and Properties of the Principal Eigenvalue of Elliptic Operators in Unbounded Domains

Using three different notions of the generalized principal eigenvalue of linear second‐order elliptic operators in unbounded domains, we derive necessary and sufficient conditions for the validity of the maximum principle, as well as for the existence of positive eigenfunctions for the Dirichlet problem. Relations between these principal eigenvalues, their simplicity, and several other properties are further discussed. © 2015 Wiley Periodicals, Inc.     

Elastizitätsmessungen an Polyacrylnitril-Lösungen

Zusammenfassung Lösungen von Polyacrylnitril (PAN) in Dimethylformamid (DMF) mit Konzentrationen von 0,05 bis 0,175 kg/l wurden in zwei Zylinder-Viskosimetern bei 22°C untersucht. Die Anlaufmessungen im Elastoviskosimeter nachLederer undSchurz, das durch einen Neubau betriebssicher gemacht wurde, ergaben eine Zunahme des Ruheschermoduls mit der vierten Potenz der Konzentration oberhalb 0,08 kg/l. Die Rückfederungsmessungen am Rotovisko mit Elastizitätsmeßzusatz der Firma Haake (wofür konstruktive Verbesserungen vorgeschlagen werden, um auch Vorgänge, die in weniger als 0,1 s ablaufen, erfassen zu können) zeigen gespeicherte Scherungen bei Deformationsgeschwindigkeiten über 10s^–1 und Konzentrationen ab 0,1 kg/l. Für Lösungen von PAN in DMF kann der Übergang vom nicht vollständig ausgeprägten Partikeltyp zum Netzwerktyp im Konzentrationsbereich um 0,08 kg/l angenommen werden.

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Summary Solutions of polyacrylonitrile (PAN) in dimethylformamide (DMF) with concentrations 0.05 to 0.175 kg/l were studied in two cylinder viscometers at 22°C. The overshoot measurements in a newly designed version of the elastoviscometer according toLederer andSchurz showed an increase of the shear modulus at rest with the fourth power of the concentration above 0.08 kg/l. Recoil measurements with the Rotovisco device (Fa. Haake; with improved design for a time constant <0.1s) showed recoverable shear elasticity at shear gradients above 10s^–1 andc 0.1 kg/l. For solutions of PAN/DMF, the transition from complete particle solution to network solution has to be assumed around 0.08 kg/l.

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Vortrag, gehalten auf der Jahrestagung der Deutschen Rheologischen Gesellschaft in Aachen vom 5.–7. März 1979.

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Mit 12 Abbildungen und 2 Tabellen     

Ein Hochdruck-Kapillarviskosimeter mit elektronischer Druckmessung

Zusammenfassung Die Konstruktion eines neuen Hochdruck-Kapillarviskosimeters wird beschrieben. Die Druckmessung erfolgt elektronisch direkt an der Meßflüssigkeit. Das Lösen von Druckgas in der Meßflüssigkeit wird verhindert. Durch Temperaturfühler vor und nach der Kapillare können Erwärmungseffekte verfolgt werden. Weitere Verbesserungsmöglichkeiten werden besprochen und einige Messungen mitgeteilt.Vorgetragen auf der Jahrestagung der Deutschen Rheologen vom 11.–13. Mai 1964 in Berlin-Dahlem.