Structural features of iron‐phosphate glass

This paper reports a study and discusses the role of Fe ions in the inhibition of corrosion of iron phosphate glasses. The structure of the 40Fe₂O₃–60P₂O₅ (mol%) glass, having a confirmed dissolution rate in aqueous solution at 90°C superior to borosilicate glasses, was investigated. Samples were crystallized at characteristic temperatures defined by differential thermal analysis and analyzed by X‐ray diffraction. Crystalline phases of Fe₂Fe[P₂O₇]₂ and Fe₄[P₂O₇]₃ were detected. The hyperfine parameters from the Mössbauer spectrum indicate that both Fe²⁺ and Fe³⁺ ions are in octahedral coordination, and 18% of the Fe³⁺ ions in the starting batch are reduced to Fe²⁺ ions after melting. The broad and symmetric spectra centered in g≈2.0 from the EPR measurements indicate the presence of two or more Fe interacting ions occupying sites of relatively high local symmetry.     

Temperature gradients in the channels of a single‐screw extruder

We used a temperature‐sensitive fluorescent dye, perylene, to monitor the true resin temperature during extrusion of polycarbonate. The measurement involved doping polycarbonate with perylene and detecting fluorescence with an optical sensor that accesses a standard instrumentation port on a barrel of a single‐screw extruder. The sensor's confocal optics design permits fluorescence intensity measurements as a function of position. Using a previously established calibration function, temperature and temperature gradients were obtained from the measured fluorescence. Because the origin of the measurement is the fluorescent dye molecule that is soluble in the resin, this method allows temperature measurement of the polymer without interference from the surrounding metal parts. With the sensor looking over the screw, temperature profiles from the barrel wall to the core of the screw were obtained as a function of screw speed, screw design and resin melt flow rate. Polym. Eng. Sci. 44:2148–2157, 2004. © 2004 Society of Plastics Engineers.

1 This paper is a contribution from the National Institute of Standards and Technology, and, thus, is not subject to copyright in the United States.

     

Dichroic nanocomposites based on polymers and metallic particles: from biology to materials science

Dichroic nanocomposites change their colors when they are viewed through a turning polarizer. In the case of polymer matrices containing inorganic nanoparticles, this color effect originates in anisotropic structures of inorganic moieties, such as uniaxially oriented linear assemblies of spherical nanoparticles or parallel oriented nanorods. The orientation of the particles or particle assemblies, respectively, is induced by the polymer matrix, either through oriented elongated hollow spaces or drawing. Matrices based on biopolymers (e.g. cellulose, polypeptides, chitin) as well as synthetic polymers (e.g. polyethylene, poly(vinyl alcohol)) have been employed. The dichroic colors have been generated so far mainly by silver or gold particles (including nanorods), but also other metals and occasionally also semiconductors (metalloids). Notably, dichroism is also disclosed in optical absorption spectra recorded with polarized light. Dichroism in biopolymer‐based objects with incorporated nanoparticles has been exploited for the cognition of biological fine structures, while dichroic films with technical polymers as matrices have been considered as optical switches in bicolored liquid crystal displays and authenticity cachets for documents, banknotes and packaging films. In this context, micropatterning of dichroic nanocomposites, which has been achieved by local heating procedures of materials composed of metal nanorods, is also of interest. © 2017 Society of Chemical Industry     

Modeling of ultrasonic processing

Curing of fiber‐reinforced thermoset polymer composites requires an elevated temperature to accelerate the crosslinking reaction and also hydrostatic pressure to consolidate the part and suppress the formation of voids. These processing conditions can be provided by autoclaves of appropriate size, but these are expensive and sometimes difficult to schedule. Ultrasonic debulking followed by oven cure is an attractive alternative to autoclave cure. In this technique a movable “horn” driven at ultrasonic frequency is applied to the surface of the uncured part. This generates pressure and at the same time produces heating by viscoelastic dissipation. The part can be debulked to net shape and staged through the action of the ultrasound. There are a large enough number of experimental parameters in ultrasonic debulking and staging to make purely empirical process optimization difficult, and this paper outlines numerical simulation methods useful in understanding and developing the process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1609–1615, 2004     

Influence of surface defects on the biaxial strength of a silicon nitride ceramic - Increase of strength by crack healing

Failure of brittle materials starts in general from defects which exist in the volume or on the surface of the specimens. Surface flaws, which are more dangerous than volume flaws, can be introduced by machining. They decrease the strength of specimens and components.For this investigation silicon nitride specimens were produced using different machining conditions. About half of them were strength tested by use of the biaxial ball-on-three balls (B3B) test. It has been shown that better (more gentle) machining increases the strength but may also cause an increased scatter of strength data.The remaining specimens were heat treated (annealed) at 1000 °C in air and afterwards also strength tested using the B3B test. Compared to the non heat treated specimens a significant increase in strength could be proven, which was - depending on the machining conditions - between almost 300 MPa and more than 500 MPa. The scatter of strength data was largely decreased.The improvement was caused by the formation of a thin (0.5-2 μm) glassy layer which filled surface cracks and surface related pores during annealing.     

Large Eddy Simulation of Turbulent Reacting Mixing of Liquids in a Coaxial Jet Mixer

Large eddy simulation is used to investigate passive and reactive scalar mixing at high Reynolds Re and Schmidt Sc numbers in order to prove capability of the LES‐SGS micromixing approaches based on the eddy dissipation and DQMOM‐IEM models properly simulating liquid reacting flows. Simulations were performed for a fast neutralization reaction in a confined jet reactor. The mean profiles for passive scalar agree well with measurements. It was shown that the most contribution to the scalar variance is made by large scale motions whereas the contribution of fine scales smaller than typical inertial range scales is negligible. Thus, the existing LES models are capable of predicting the scalar variance at large Sc numbers. The results obtained for reactive transport revealed discrepancies in the determination of micromixing rate and product concentration. A special study was performed to investigate the dynamics of fine structures using locally refined box embedded into global grid. Typical statistical properties of fine structures were reproduced numerically.     

Selective Covalent Protein Modification by 4‐Halopyridines through Catalysis

We have investigated 4‐halopyridines as selective, tunable, and switchable covalent protein modifiers for use in the development of chemical probes. Nonenzymatic reactivity of 4‐chloropyridine with amino acids and thiols was ranked with respect to common covalent protein‐modifying reagents and found to have reactivity similar to that of acrylamide, but could be switched to a reactivity similar to that of iodoacetamide upon stabilization of the positively charged pyridinium. Diverse, fragment‐sized 4‐halopyridines inactivated human dimethylarginine dimethylaminohydrolase‐1 (DDAH1) through covalent modification of the active site cysteine, acting as quiescent affinity labels that required off‐pathway catalysis through stabilization of the protonated pyridinium by a neighboring aspartate residue. A series of 2‐fluoromethyl‐substituted 4‐chloropyridines demonstrated that the pK_a and k_inact/K_I values could be predictably varied over several orders of magnitude. Covalent labeling of proteins in an Escherichia coli lysate was shown to require folded proteins, indicating that alternative proteins can be targeted, and modification is likely to be catalysisdependent. 4‐Halopyridines, and quiescent affinity labels in general, represent an attractive strategy to develop reagents with switchable electrophilicity as selective covalent protein modifiers.     

Metal-Sulfate Induced Generation of ROS in Human Brain Cells: Detection Using an Isomeric Mixture of 5- and 6-Carboxy-2',7'-Dichlorofluorescein Diacetate (Carboxy-DCFDA) as a Cell Permeant Tracer

Evolution of reactive oxygen species (ROS), generated during the patho-physiological stress of nervous tissue, has been implicated in the etiology of several progressive human neurological disorders including Alzheimer's disease (AD) and amylotrophic lateral sclerosis (ALS). In this brief communication we used mixed isomers of 5-(and-6)-carboxy-2',7'-dichlorofluorescein diacetate (carboxy-DCFDA; C(25)H(14)C(l2)O(9); MW 529.3), a novel fluorescent indicator, to assess ROS generation within human neuronal-glial (HNG) cells in primary co-culture. We introduced pathological stress using the sulfates of 12 environmentally-, industrially- and agriculturally-relevant divalent and trivalent metals including Al, Cd, Cu, Fe, Hg, Ga, Mg, Mn, Ni, Pb, Sn and Zn. In this experimental test system, of all the metal sulfates analyzed, aluminum sulfate showed by far the greatest ability to induce intracellular ROS. These studies indicate the utility of using isomeric mixtures of carboxy-H(2)DCFDA diacetates as novel and highly sensitive, long-lasting, cell-permeant, fluorescein-based tracers for quantifying ROS generation in intact, metabolizing human brain cells, and in analyzing the potential epigenetic contribution of different metal sulfates to ROS-generation and ROS-mediated neurological dysfunction.