Controlling microstructure and film growth of relaxor-ferroelectric thin films for high break-down strength and energy-storage performance

The relaxor ferroelectric Pb_0.9La_0.1(Zr_0.52Ti_0.48)O₃ (PLZT) thin films were deposited using pulsed laser deposition, and their microstructures, break-down field strengths and energy storage performances were investigated as a function of the buffer layer and electrode. A large recoverable energy-storage density (U_reco) of 23.2 J/cm³ and high energy-storage efficiency (η) of 91.6% obtained in the epitaxial PLZT film grown on SrRuO₃/SrTiO₃/Si are much higher than those in the textured PLZT film (U_reco = 21.9 J/cm³, η = 87.8%) on SrRuO₃/Ca₂Nb₃O₁₀-nanosheet/Si and the polycrystalline PLZT film (U_reco = 17.6 J/cm³, η = 82.6%) on Pt/Ti/SiO₂/Si, under the same condition of 1500 kV/cm and 1 kHz, due to the slim polarization loop and significant antiferroelectric-like behavior. Owing to the high break-down strength (BDS) of 2500 kV/cm, a giant U_reco value of 40.2 J/cm³ was obtained for the epitaxial PLZT film, in which U_reco values of 28.4 J/cm³ (at BDS of 2000 kV/cm) and 20.2 J/cm³ (at BDS of 1700 kV/cm), respectively, were obtained in the textured and polycrystalline PLZT films. The excellent fatigue-free properties and high thermal stability were also observed in these films.     

Swelling behavior of polymeric membranes to metalworking fluids

In some working places, such as metal manufacturing or automotive services, mechanical hazards commonly occur along with chemical hazards, particularly metalworking fluids (MWFs). The presence of these chemicals could modify the properties of gloves made from polymeric materials and thus reduce their protective properties against chemical contamination (solvent, MWFs) and mechanical risks (puncture and cutting). This work focused on determining the swelling characteristics and the resistance of six polymeric membranes which were exposed to seven industrial MWFs. We found that the swelling tests can be used to classify the potential of coating polymers in descending order of their resistance to MWFs: nitrile, polyurethane > poly(vinyl chloride), neoprene > butyl, latex. The analysis by multiple linear regression showed, for the first time, that the density or the viscosity‐gravity constant of the fluid and Hansen's solubility parameters of the polymers have a significant impact on the swelling of polymer. For the first time, two new multiple regression models have been proposed, to predict the swelling phenomena of polymers under various MWFs with an accuracy of ≈80%. The effect of temperature on mechanical properties and morphology of material was also examined. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45717.     

Methane aromatization over Mo/H-ZSM-5: on the reaction pathway

Rates of benzene formation on Mo/HZSM-5, H-ZSM-5 and Mo/SiO₂ were measured with different reactants: methane, mixture of C₂H₄/H₂/N₂ and mixture of C₂H₂/H₂/N₂. Since the rate of benzene formation starting from C₂H₄/H₂/N₂ is higher on Mo/H-ZSM-5 compared to H-ZSM-5 it is concluded that the aromatization of methane on Mo/H-ZSM-5 is not going via ethylene which is aromatized over acid sites. Another reaction pathway is proposed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Fluorinated siloxane amine oligomers

Fluorine‐containing siloxane oligomers were made from bis(aminopropyl)tetramethyldisiloxane and trimethyltris(trifluoropropyl)cyclotrisiloxane. These materials were characterized by IR spectroscopy, size exclusion chromatography, nonaqueous colorimetric end group titration, and ¹H‐NMR. The end groups of one oligomer were chemically modified for an increased NMR signal for molecular weight determination. The cyclic trimeric siloxane starting material was additionally studied via ¹³C‐, ²⁹Si‐, and ¹⁹F‐NMR. Two forms of it were used: a white solid obtained at room temperature, and a colorless liquid isolated at low temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1315–1320, 2000     

Corrosion protection of molybdate doped polypyrrole film prepared in succinic acid solution

ABSTRACT

Polypyrrole (PPy) was prepared on the mild steel substrate by electrochemical polymerisation in the solution containing pyrrole monomer and succinic acid. The mild steel surface could be passivated before and during electropolymerisation by molybdate. The morphology and structure of the PPy film were studied with SEM. The typical cauliflower structure of PPy was observed. Raman and IR spectroscopy showed that the obtained PPy was in an oxidised state. The thermal stability of PPy was investigated by the thermal gravimetric analysis, showing that PPy was stable at higher than 480°C. The electrochemical property of the PPy film was performed by open circuit potential, polarisation curves (I/E), and electrochemical impedance spectroscopy. The corrosion behaviour of mild steel (CT3) with PPy film in solution NaCl 3% was studied.

This paper is part of a supplementary issue from the 17th Asia-Pacific Corrosion Control Conference (APCCC-17).     

Thermal aging of a blend of high‐performance fibers

The focus of this work is the study of the thermal aging of high‐performance fibers used in the making of fire protective garments. Accelerated thermal aging tests were carried out on fabric samples made up of a blend of Kevlar® (poly p‐phenylene terephthalamide) and PBI (poly benzimidazole) staple fibers, as well as on yarns pulled from this fabric, by means of exposure to elevated temperatures, comprised between 190°C and 320°C. All samples underwent loss of breaking force retention. The material thermal life, defined as the time required for the fibers to attain a 50% reduction of the original breaking force, ranged between a dozen of days at the lowest exposure temperature, to less than an hour at the highest. Breaking force data were fitted using the Arrhenius model following two different approaches, namely the extrapolated thermal life value and the shift factors yielded by the time‐temperature superposition (TTS). The Arrhenius model seemed to describe appropriately the overall aging process, as inferred from the excellent fit obtained when using both approaches, although activation energies provided from both approaches are different. To follow the chemical evolution of the material with thermal aging, Fourier‐transform infrared (FTIR) analyses were conducted. The qualitative analysis of the FTIR spectra showed little evidence of chemical changes between the aged and the nonaged samples, indicating either that the aging process carries on without significant modification of the chemical structure of the fibers, or that FTIR is not an appropriate method to spot such a modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Soluble Prokaryotic Overexpression and Purification of Human GM-CSF Using the Protein Disulfide Isomerase b′a′ Domain

Granulocyte-macrophage colony-stimulating factor (GM-CSF) is a member of the colony-stimulating factor (CSF) family, which functions to enhance the proliferation and differentiation of hematopoietic stem cells and other hematopoietic lineages such as neutrophils, dendritic cells, or macrophages. These proteins have thus generated considerable interest in clinical therapy research. A current obstacle to the prokaryotic production of human GM-CSF (hGM-CSF) is its low solubility when overexpressed and subsequent complex refolding processes. In our present study, the solubility of hGM-CSF was examined when combined with three N-terminal fusion tags in five E. coli strains at three different expression temperatures. In the five E. coli strains BL21 (DE3), ClearColi BL21 (DE3), LOBSTR, SHuffle T7 and Origami2 (DE3), the hexahistidine-tagged hGM-CSF showed the best expression but was insoluble in all cases at each examined temperature. Tagging with the maltose-binding protein (MBP) and the b′a′ domain of protein disulfide isomerase (PDIb′a′) greatly improved the soluble overexpression of hGM-CSF at 30 °C and 18 °C. The solubility was not improved using the Origami2 (DE3) and SHuffle T7 strains that have been engineered for disulfide bond formation. Two conventional chromatographic steps were used to purify hGM-CSF from the overexpressed PDIb′a′-hGM-CSF produced in ClearColi BL21 (DE3). In the experiment, 0.65 mg of hGM-CSF was isolated from a 0.5 L flask culture of these E. coli and showed a 98% purity by SDS-PAGE analysis and silver staining. The bioactivity of this purified hGM-CSF was measured at an EC₅₀ of 16.4 ± 2 pM by a CCK8 assay in TF-1 human erythroleukemia cells.     

Thermomechanical postbuckling behavior of CNT-reinforced composite sandwich plate models resting on elastic foundations with elastically restrained unloaded edges

Buckling and postbuckling behaviors of two models of sandwich plate reinforced by carbon nanotubes (CNTs) resting on elastic foundations and subjected to uniaxial compressive and thermomechanical loads are investigated in this paper. Material properties of all constituents are assumed to be temperature dependent and effective properties of CNT-reinforced composite layer are determined according to extended rule of mixture. Governing equations are established within the framework of first-order shear deformation theory taking into account von Kármán nonlinearity, initial geometrical imperfection, plate-foundation interaction and tangential elastic constraints of unloaded edges. Three types of loading are considered including uniaxial compression, preexisting thermal load combined with uniaxial compression and preexisting mechanical load combined with thermal load. Approximate analytical solutions are assumed to satisfy simply supported boundary conditions and the Galerkin method is used to derive nonlinear load-deflection relations from which buckling loads and postbuckling equilibrium paths are determined. The most important findings are that tangential constraints of unloaded edges significantly lowers buckling loads and postbuckling load capacity of sandwich plates and, in contrast, buckling loads and postbuckling strength are considerably enhanced as sandwich plate is constructed from CNT-reinforced composite core layer and homogeneous face sheets.     

Mild-Heat and High-Pressure Inactivation of Carrot Pectin Methylesterase: A Kinetic Study

ABSTRACT: Pectin methylesterase (PME) was extracted from carrots and purified by affinity chromatography. The thermal high-pressure inactivation of the PME was investigated in a model system. Under these conditions, the (thermo) stable fraction is not inactivated and the isobaric-isothermal inactivation followed a fractional-conversion model. At lower pressures (< 300 MPa) and higher temperatures (> 50°C), an antagonistic effect of pressure and heat was observed. A 2nd- and 3rd-degree polynomial model (derived from available thermodynamic model) was successfully used to describe the heat pressure dependence of the inactivation rate constants. From the purified carrot PME sample, the thermostable PME fraction was isolated. The thermal inactivation of this fraction followed first-order kinetics.     

Kinetics and mechanistic aspects of As(III) oxidation by aqueous chlorine, chloramines, and ozone: relevance to drinking water treatment

Kinetics and mechanisms of As(III) oxidation by free available chlorine (FAC-the sum of HOCl and OCl-), ozone (O3), and monochloramine (NH2Cl) were investigated in buffered reagent solutions. Each reaction was found to be first order in oxidant and in As(III), with 1:1 stoichiometry. FAC-As(III) and O3-As(III) reactions were extremely fast, with pH-dependent, apparent second-order rate constants, k'app, of 2.6 (+/- 0.1) x 10(5) M(-1) s(-1) and 1.5 (+/- 0.1) x 10(6) M(-1) s(-1) at pH 7, whereas the NH2Cl-As(III) reaction was relatively slow (k'app = 4.3 (+/- 1.7) x 10(-1) M(-1) s(-1) at pH 7). Experiments conducted in real water samples spiked with 50 microg/L As(III) (6.7 x 10(-7) M) showed that a 0.1 mg/L Cl2 (1.4 x 10-6 M) dose as FAC was sufficient to achieve depletion of As(III) to <1 microg/L As(III) within 10 s of oxidant addition to waters containing negligible NH3 concentrations and DOC concentrations <2 mg-C/L. Even in a water containing 1 mg-N/L (7.1 x 10(-5) M) as NH3, >75% As(III) oxidation could be achieved within 10 s of dosing 1-2 mg/L Cl2 (1.4-2.8 x 10(-5) M) as FAC. As(III) residuals remaining in NH3-containing waters 10 s after dosing FAC were slowly oxidized (t1/2 > or = 4 h) in the presence of NH2Cl formed by the FAC-NH3 reaction. Ozonation was sufficient to yield >99% depletion of 50 microg/L As(III) within 10 s of dosing 0.25 mg/L O3 (5.2 x 10(-6) M) to real waters containing <2 mg-C/L of DOC, while 0.8 mg/L O3 (1.7 x 10(-5) M) was sufficientfor a water containing 5.4 mg-C/L of DOC. NH3 had negligible effect on the efficiency of As(III) oxidation by O3, due to the slow kinetics of the O3-NH3 reaction at circumneutral pH. Time-resolved measurements of As(III) loss during chlorination and ozonation of real waters were accurately modeled using the rate constants determined in this investigation.