Multivariate process trajectories for molecular description of MF thermal curing and correlation with hydrolytic stability

During curing of thermosetting resins the technologically relevant properties of binders and coatings develop. However, curing is difficult to monitor due to the multitude of chemical and physical processes taking place. Precise prediction of specific technological properties based on molecular properties is very difficult. In this study, the potential of principal component analysis (PCA) and principal component regression (PCR) in the analysis of Fourier transform infrared (FTIR) spectra is demonstrated using the example of melamine-formaldehyde (MF) resin curing in solid state. FTIR/PCA-based reaction trajectories are used to visualize the influence of temperature on isothermal cure. An FTIR/PCR model for predicting the hydrolysis resistance of cured MF resin from their spectral fingerprints is presented which illustrates the advantages of FTIR/PCR compared to the combination differential scanning calorimetry/isoconversional kinetic analysis. The presented methodology is transferable to the curing reactions of any thermosetting resin and can be applied to model other technologically relevant final properties as well.     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

α-Alumina and spinel react into single-phase high-alumina spinel in <3 seconds during flash sintering

In situ X-ray diffraction measurements at the Advanced Photon Source show that α-Al₂O₃ and MgAl₂O₄ react nearly instantaneously and completely, and nearly completely to form single-phase high-alumina spinel during voltage-to-current type of flash sintering experiments. The initial sample was constituted from powders of α-Al₂O₃, MgAl₂O₄ spinel, and cubic 8 mol% Y₂O₃-stabilized ZrO₂ (8YSZ) mixed in equal volume fractions, the spinel to alumina molar ratio being 1:1.5. Specimen temperature was measured by thermal expansion of the platinum standard. These measurements correlated well with a black-body radiation model, using appropriate values for the emissivity of the constituents. Temperatures of 1600-1736°C were reached during the flash, which promoted the formation of alumina-rich spinel. In a second set of experiments, the flash was induced in a current-rate method where the current flowing through the specimen is controlled and increased at a constant rate. In these experiments, we observed the formation of two different compositions of spinel, MgO•3Al₂O₃ and MgO•1.5Al₂O₃, which evolved into a single composition of MgO•2.5Al₂O₃ as the current continued to increase. In summary, flash sintering is an expedient way to create single-phase, alumina-rich spinel.     

Effect of silane structure on the properties of silanized multiwalled carbon nanotube-epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were functionalized with aminosilanes via an aqueous deposition route. The size and morphology of siloxane oligomers grafted to the MWCNTs was tuned by varying the silane functionality and concentration and their effect on the properties of a filled epoxy system was investigated. The siloxane structure was found to profoundly affect the thermo-mechanical behavior of composites reinforced with the silanized MWCNTs. Well-defined siloxane brushes increased the epoxy T_g by up to 19 °C and significantly altered the network relaxation dynamics, while irregular, siloxane networks grafted to the MWCNTs had little effect. The addition of both types of silanized MWCNTs elicited improvements in the strength of the nanocomposites, but only the well-defined siloxane brushes engendered dramatic improvements in toughness. Because the silanization reaction is simple, rapid, and performed under aqueous conditions, it is also an industrially attractive functionalization route.     

The Fight against the Influenza A Virus H1N1: Synthesis,Molecular Modeling,and Biological Evaluation of Benzofurazan Derivatives as Viral RNA Polymerase Inhibitors

The influenza RNA polymerase complex, which consists of the three subunits PA, PB1, and PB2, is a promising target for the development of new antiviral drugs. A large library of benzofurazan compounds was synthesized and assayed against influenza virus A/WSN/33 (H1N1). Most of the new derivatives were found to act by inhibiting the viral RNA polymerase complex through disruption of the complex formed between subunits PA and PB1. Docking studies were also performed to elucidate the binding mode of benzofurazans within the PB1 binding site in PA and to identify amino acids involved in their mechanism of action. The predicted binding pose is fully consistent with the biological data and lays the foundation for the rational development of more effective PA–PB1 inhibitors.     

Highly Porous Geopolymers Through Templating and Surface Interactions

The natural porosity of geopolymers and the simplicity of geopolymer synthesis make them a potential candidate for the formation of highly porous ceramics. Here, the synthesis of highly porous (≈70 vol% or more) metakaolin geopolymer is demonstrated using a novel emulsion preparation with one‐pot curing and hydrophobization of the interior pores with alkylalkoxysilanes. Using mercury intrusion porosimetry, tailoring of the characteristic percolation pore size is demonstrated over a range of ≈200 nm to 10 μm. Using powder X‐ray diffraction, reactivity was shown to be decreased versus typical geopolymers, but substantial geopolymerization still occurred and the samples formed cohesive monoliths. Optional calcination under inert conditions allowed for formation of a glassy ceramic with a notable SiC phase, as well as further increasing the porosity by removing the hydrophobic pore coatings.     

Energy storage in symmetric and asymmetric supercapacitors based in carbon cloth/polyaniline–carbon black nanocomposites

In this work, the construction of electrochemical capacitors using polyaniline–carbon black nanocomposites as electrode material is described. Symmetric and asymmetric cells were assembled. The active material was supported on carbon cloth acting as current collector as well. The electrolyte was H₂SO₄ 0.5 M, and the selected potential range was 1 V. The electrochemical behavior of the arrayed supercapacitors was studied by cyclic voltammetry and galvanostatic charge/discharge runs. At a constant current density of 0.3 A/g, a specific capacitance value of 1039 F/g was obtained for a symmetric assembly using both electrodes prepared with polyaniline and carbon black nanocomposites. When the set is asymmetric, being the positive electrode made of polyaniline and carbon black nanocomposites, the specific capacitance value is 1534 F/g. For the latter array, the specific power and energy density values are 300 W/kg and 426 Wh/kg at 0.3 A/g, and 13 700 W/kg and 28 Wh/kg at 13.7 A/g. These results suggest a good capacity of fast energy transfer. Moreover, this asymmetric supercapacitor demonstrated a high stability over 1000 cycles being the loss of only 5%. Copyright © 2015 John Wiley & Sons, Ltd.     

The Indianization of Colonial Medicine

ZUSAMMENFASSUNG: Anders als die weitgehend in der Geschichtsschreibung belegte psychiatrische Anstalt für Europ?er und Europ?erinnen mit ihrem englischen Leiter Owen Berkeley-Hill ist die weitaus gr??ere Institution für indische Patienten und Patientinnen im nordindischen Ranchi bisher nicht untersucht worden. Im Mittelpunkt dieses Beitrags steht die Karriere des Leiters dieser Institution, Jal E. Dhunjibhoy, zu Beginn des 20. Jahrhunderts als von der britischen Kolonialregierung eine Indianisierung der medizinischen Einrichtungen angestrebt wurde. Im Gegensatz zu bisherigen Studien über intermediaries und middles konzentriert sich dieser Aufsatz auf einen hochrangigen einheimischen Mitarbeiter. Die verbreitete Annahme zwangsl?ufiger historischer Prozesse wird dabei differenziert, eine regionale Kontextualisierung vorgenommen und die Kontinuit?t offener und versteckter Diskriminierung indischer Mediziner in Bezug auf Entlohnung, gesellschaftliche Stellung, fachliche Anerkennung, posthume Würdigung und historiographischer Berücksichtigung herausgearbeitet. Es wird verdeutlicht, in welcher Weise koloniale Akteure in bestehende gesellschaftliche Disparit?ten und soziopolitische Prozessen verstrickt waren und wie die Karriere eines leitenden Mediziners von einer Vielzahl von au?ermedizinischen Zusammenh?ngen bestimmt wurde. Gleichzeitig wird hervorgehoben, dass ihre strukturelle Positionierung als inbetweens, Kollaborateure oder Repr?sentanten einer erfolgreichen Dekolonisierung für ein nuancierteres Verst?ndnis ihrer beruflichen und pers?nlichen Identit?tsformierung nicht ausreicht.