Carbon radicals generated by solid polymers: Electron spin resonance spectroscopy for detection of species in water

Radicals generated in plastic medical devices (solid phase) by γ-rays or electron-beam irradiation during sterilization are known to cause oxidation of protein drugs, resulting in a loss or reduction in drug efficacy. The generation of radical species in water by the radical species in solid polymers has not been proved. Using electron spin resonance (ESR) spectroscopy, we confirm the generation of new radicals in water by γ-ray irradiated cyclic olefin polymers (COP). ESR measurements are obtained using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) as a spin probe and 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO) as a spin trap, in which the irradiated COP was immersed. The ESR signals indicate the TEMPOL radicals decline over time, suggesting the generation of new radicals. Conversely, the characteristic ESR signals of the adduct formed by the reaction between CYPMPO and the hydroxyl radical are observed. Thus, hydroxyl radicals are generated because of the migration of the radicals from COP to water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48604.     

Effect of Deposition Rate on the Stress Evolution of Plasma-Sprayed Yttria-Stabilized Zirconia

The deposition rate plays an important role in determining the thickness, stress state, and physical properties of plasma-sprayed coatings. In this article, the effect of the deposition rate on the stress evolution during the deposition (named evolving stress) of yttria-stabilized zirconia coatings was systematically studied by varying the powder feed rate and the robot-scanning speed. The evolving stress during the deposition tends to increase with the increased deposition rate, and this tendency was less significant at a longer spray distance. In some cases, the powder feed rate had more significant influence on the evolving stress than the robot speed. This tendency can be associated with a deviation of a local deposition temperature at a place where sprayed particles are deposited from an average substrate temperature. At a further higher deposition rate, the evolving stress was relieved by introduction of macroscopic vertical cracks as well as horizontal branching cracks.     

Mitigation of damage from molten fly ash to air-plasma-sprayed thermal barrier coatings

Ceramic thermal barrier coatings (TBCs) used in gas-turbine engines afford higher operating temperatures, resulting in enhanced efficiencies and performance. However, in the case of syngas-fired engines, fly ash particulate impurities that may be present in syngas can melt on the hotter TBC surfaces and form glassy deposits. These deposits can penetrate the TBCs leading to their failure. In experiments using lignite fly ash to simulate these conditions we show that conventional TBCs of composition 93 wt% ZrO₂ + 7 wt% Y₂O₃ (7YSZ) fabricated using the air plasma spray (APS) process are completely destroyed by the molten fly ash. The molten fly ash is found to penetrate the full thickness of the TBC. The mechanisms by which this occurs appear to be similar to those observed in degradation of 7YSZ TBCs by molten calcium-magnesium-alumino-silicate (CMAS) sand and by molten volcanic ash in aircraft engines. In contrast, APS TBCs of Gd₂Zr₂O₇ composition are highly resistant to attack by molten lignite fly ash under identical conditions, where the molten ash penetrates ∼25% of TBC thickness. This damage mitigation appears to be due to the formation of an impervious, stable crystalline layer at the fly ash/Gd₂Zr₂O₇ TBC interface arresting the penetrating molten-fly-ash front.     

Synergistic Extraction of Am(III) and Eu(III) by Tris(2‐pyridylmethyl)Amine with Various Anions in 1,2‐Dichloroethane

The extraction equilibria of Am(III) and Eu(III) by using a tripodal ligand, tris(2‐pyridylmethyl)amine (tpa), with various lipophilic anions have been investigated. The extractability of both Am(III) and Eu(III) was increased by the combination of tpa and counteranions due to a synergistic effect. The separation factors between Am(III) and Eu(III) were also increased from 7.6 to 49 by the combination of counteranions and organic solvents. The extraction equilibria of Am(III) and Eu(III) with tpa in 1,2‐dichloroethane were determined by slope analysis. It was found that three anions and one molecule of the ligand coordinated to Am(III) and Eu(III) was extracted regardless of the anions.     

Effect of CaO Addition on Compressive Deformation of Silicon Nitride Ceramic with Y‐Mg‐Si‐O‐N Glassy System

Creep behavior of Si₃N₄ polycrystals containing Y₂O₃‐MgO‐SiO₂ glass phase (with and without Calcium oxide [CaO] additive) was studied by compression tests between 1500 and 1700°C. We studied the effect of CaO additive on flow stress, microstructural evolutions, and thermal stability of the intergranular glass phase during deformation. While the addition of CaO did not affect grain size, the flow stress decreased with the amount of CaO. This result suggested that the addition of CaO reduced the viscosity of intergranular glass phase. The addition of CaO further improved the thermal stability of the glass phase by suppressing the evaporation at elevated temperatures.     

A 30,000-cd/m2, 50-lm/W,and 92%-luminance-uniformity flat discharge fluorescent lamp for LCD backlights

Abstract— A 5.2-in.-diagonal simple-structured argon-mercury cold-cathode flat discharge fluorescent lamp has been developed for LCD backlighting. A pair of insulated electrodes is provided at the top and bottom ends of the inner surface of the front glass plate. Phosphor is deposited on both the front and rear glass plates. A luminance of 30,000 cd/m² and a luminous efficacy of 50 lm/W were obtained with a luminance uniformity of 92% without the use of a diffuser sheet. A mechanism for obtaining the high luminous efficacy is described. Luminance can be dimmed down to 4% of the peak value by extending the pulse interval and/or by reducing the pulse amplitude.     

A chimeric inorganic pyrophosphatase derived from Escherichia coli and Thermus thermophilus has an increased thermostability

Factors contributing to the thermostability of inorganic pyrophosphatase (PPase) were investigated by examining chimeric PPases from Escherichia coli and Thermus thermophilus (Tth). Two chimeric PPase genes, T1-135E (residues 1-135 from the N terminus are comprised of Tth PPase and residues 136-173 are derived from the C terminus of E. coli PPase) and T1-149E [residues 1-149 from the N terminus are from Tth PPase and the rest (150-175) are from E. coli PPase], were constructed by random chimeragenesis. After the genes were overexpressed in the E. coli BL21(DE3) strain and the expression products were purified, we compared the characteristics of these chimeric PPases with those of the parental PPases. We found that the two chimeras had higher activity than either parent PPase at the optimum temperature. We also examined thermal stability in terms of CD spectra, fluorescence spectra, and thermal changes in enzyme activity. The results revealed that the thermal stability of T1-149E is similar to that of Tth PPase, but T1-135E is much more stable. This suggests that the four residues that are different between T1-135E and T1-149E may be critical for thermostability between the two chimeras. By comparing the three-dimensional structures of Tth and E. coli PPases, we deduced that the following two factors may contribute to differences in thermostability. (1) Two residues (Thr138 and Ala141 in the Tth PPase and His140 and Asp143 in the E. coli PPase) in the vicinity of the trimer-trimer interface were different. (2) The Ala144-Lys145 loop in the Tth PPase was deleted in the E. coli PPase and also in the T1-135E chimera. Therefore, we conclude that T1-135E was thermostabilized by these two factors, and also, the Tth PPase moiety may contribute to the structural integrity of the chimeric enzymes.     

Influence of phosphate species on green rust I transformation and local structure and morphology of γ-FeOOH

To clarify the role of phosphate in the formation of corrosion products, the transformation of GRI(Cl⁻) with the addition of phosphate was characterized through XRD, TEM, and solution analysis. Electrochemical analysis showed that the transformation of GRI(Cl⁻) was delayed and the size of the final products, i.e., γ-FeOOH was reduced in the phosphate added case. X-ray absorption spectroscopy indicated that the neighboring Fe–Fe coordination number of FeO₆ octahedral unit in γ-FeOOH was decreased. These effects of phosphate are attributed to its adsorption on GRI(Cl⁻) and nucleated γ-FeOOH that prevented particle growth during oxidation process.     

Processing effects on in-flight particle state and functional coating properties of plasma-sprayed manganese zinc ferrite

Magnetic properties of manganese zinc ferrite (MZF) coatings deposited by atmospheric dc plasma spraying largely depend on zinc and oxygen loss during particle flight. The temperature and velocity of in-flight MZF particles were widely varied by changing plasma spray conditions to examine these chemistry changes and resultant magnetic properties. Zn loss increases with increased particle temperature or decreased particle velocity. Meanwhile, wüstite (FeO) formation, related to the oxygen loss, is more complicated, partly because oxygen, which is lost during flight in the high-temperature zone of the plasma jet, can be recovered at longer spray distances. As a result, the saturation magnetization of MZF coatings decreases and the coercivity increases with increased particle temperature or decreased particle velocity.     

Oxidation of green rust suspensions containing different chromium ion species

The oxidation of hydrosulphate green rust (GR2(SO₄²⁻)) suspension containing different chromium ion species was investigated by X-ray diffraction, X-ray absorption spectroscopy and transmission electron microscopy. The pH, oxidation-reduction potential and amount of dissolved oxygen in aqueous solutions were measured during the reactions. The results show that the addition of Cr(III)₂(SO₄)₃ solution suppresses the transformation of GR2(SO₄²⁻) into iron oxyhydroxides and oxides in aqueous solution, while the addition of Na₂Cr(VI)O₄ solution promotes the transformation of GR2(SO₄²⁻) in which Cr(VI) is reduced to Cr(III); α-FeOOH particles were refined by the addition of the chromium ions.