Flash Latex Production in a Continuous Helical Photoreactor: Releasing the Brake Pedal on Acrylate Chain Radical Polymerization

The continuous photopolymerization of acrylate and methacrylate monomer miniemulsions (25% solids content) is investigated at room temperature in a compact helix minireactor. Using n‐butyl acrylate, the process yields 95% conversion after only 27 s residence time, and gel‐free high‐molecular‐weight products. Under optimized conditions, a 25‐fold increase in efficiency is obtained when compared to a batch photopolymerization. The reaction set‐up offers a frugal process because of moderate irradiance (2.6 mW cm^?2), photoinitiator concentration (0.75 wt%), and low‐power UV‐A fluorescent lamp.

     

Systematic Study of Quaternary Ammonium Cations for Bromine Sequestering Application in High Energy Density Electrolytes for Hydrogen Bromine Redox Flow Batteries

Bromine complexing agents (BCAs) are used to reduce the vapor pressure of bromine in the aqueous electrolytes of bromine flow batteries. BCAs bind hazardous, volatile bromine by forming a second, heavy liquid fused salt. The properties of BCAs in a strongly acidic bromine electrolyte are largely unexplored. A total of 38 different quaternary ammonium halides are investigated ex situ regarding their properties and applicability in bromine electrolytes as BCAs. The focus is on the development of safe and performant HBr/Br₂/H₂O electrolytes with a theoretical capacity of 180 Ah L⁻¹ for hydrogen bromine redox flow batteries (H₂/Br₂-RFB). Stable liquid fused salts, moderate bromine complexation, large conductivities and large redox potentials in the aqueous phase of the electrolytes are investigated in order to determine the most applicable BCA for this kind of electrolyte. A detailed study on the properties of BCA cations in these parameters is provided for the first time, as well as for electrolyte mixtures at different states of charge of the electrolyte. 1-ethylpyridin-1-ium bromide [C2Py]Br is selected from 38 BCAs based on its properties as a BCA that should be focused on for application in electrolytes for H₂/Br₂-RFB in the future.     

d-xylose-based bolaamphiphiles: Synthesis and influence of the spacer nature on their interfacial and membrane properties

A two-step synthesis, with good yields, of d-xylose-based bolaamphiphiles is described. The monolayer properties, the adsorption behavior and membrane destabilization properties of two bolaamphiphiles differing by their spacers (presence or absence of one double bond) were studied. The presence of one unsaturation has no influence on the interfacial organization at low compression but impairs the stability of the monolayer at high compression. Saturated and unsaturated molecules are suggested to adopt a loop structure at the interface at low compression. The higher degree of freedom of the saturated hydrophobic spacer does not affect the initial diffusion step of the bolaform from the subphase to the interface but greatly slows the arrangement step at the interface. However, once at the interface, their surface-active properties are similar. The higher flexibility of the saturated analogue spacer also greatly increases its lipid vesicle destabilizing property. Its rearrangement within the lipid bilayer is in favour of the formation of inverted phases, facilitating membrane fusion.     

Synchrotron Radiation and Neutrons in Art and Archaeology (SR2A) Conference 2016

The seventh edition of the international conference on Synchrotron Radiation and Neutrons in Art and Archaeology (SR2A 2016) was held September 6–8, 2016, at the Stock Exchange Room of The Art Institute of Chicago, USA. The conference was jointly organized by seven research laboratories and museums; more precisely, the Center for Scientific Studies in the Arts (NU-ACCESS) of Northwestern University, the Art Institute of Chicago, the Field Museum Chicago, the Advanced Photon Source (APS), the Oriental Institute Chicago, the Detroit Institute of Arts, and the Indianapolis Museum of Art, in close interaction with the SR2A International Committee. Nine years after the organization of the first SR2A conference in Grenoble, the Art Institute hosted the second biennial interdisciplinary meeting in the US.     

Photoinduced adsorption of hydrogen and methane on gamma-alumina. the photoinduced chesorluminescence (PhICL) effect

Adsorption of hydrogen and methane on a preirradiated surface of gamma-Al2O3 produces an afterglow, which has been described as a photoinduced chesorluminescence (PhICL), whose spectral features identify with the intrinsic photoluminescence of alumina. The emission spectrum consists of at least four overlapping single emission bands. For methane adsorption, the PhICL phenomenon is seen only if the solid is preirradiated in the presence of oxygen. Emission decay kinetics of the PhICL effect for gamma-Al2O3 reveal two wavelength regimes: a short wavelength regime at lambda = 300-370 nm (decay time tau = 1.1 +/- 0.2 s; signal width = 2.8 s), and a longer wavelength regime at lambda = 380-700 nm (decay time tau = 2.1 +/- 0.1 s; signal width = 4.3 s). A model is proposed in which there exist two different emission centers and, thus, two different pathways for emission decay. In the first, emission originates with electron trapping by such deep energy traps as anion vacancies {e- + Va --> F+ + hv1} to yield electron F-type color centers, whereas in the second, emission originates from electron/trapped hole recombination {e- + Os*- --> Os2- + hv2}. The first common step of the pathways is homolytic dissociative chemisorption of hydrogen and methane upon interaction with surface-active hole centers Os*-, produced upon preirradiation of alumina, to give atomic hydrogen H* and methyl radicals CH3*. Thermoprogrammed desorption spectra of photoadsorbed or postsorbed oxygen show that adsorbed oxygen interacts with atomic hydrogen and methyl radicals. The products of thermodesorption were H2O for hydrogen and H2O, CO2, and CH3CH3 for methane. The Solonitsyn memory effect coefficient was also evaluated for oxygen photoadsorption.     

Effect of surface photoreactions on the photocoloration of a wide band gap metal oxide: probing whether surface reactions are photocatalytic

A nonphotocatalytic reaction occurring on the surface of an irradiated wide band gap metal oxide, such as ZrO2, can affect the process of photoinduced formation of Zr3+, F- and V-type color centers. The effect of such reactions is seen as the influence of photostimulated adsorption on the photocoloration of the metal oxide specimen. In particular, photoadsorption of electron donor molecules leads to an increase of electron color centers, whereas photoadsorption of electron acceptor molecules leads to an increase of hole color centers. Monitoring the photocoloration of a metal oxide during a surface photochemical reaction probes whether the reaction is photocatalytic: accordingly, the influence of simple photoreactions on the photocoloration of ZrO2, reactions that involved the photoreduction of molecular oxygen, the photooxidation of molecular hydrogen, the photooxidation of hydrogen by adsorbed oxygen, and the photoinduced transformation of ammonia and carbon dioxide. Kinetics of the photoprocesses are reported, as well as the photoinduced chesorluminscence (PhICL effect) of ammonia. Thermoprogrammed desorption and mass spectral monitoring of the photoreaction involving NH3 identified hydrazine as an intermediate and molecular nitrogen as the final product. The photoreactions involving NH3 and CO2 are nonphotocatalytic processes, in contrast to the photooxidation of hydrogen which is photocatalytic. Carbon dioxide and carbonate radical anions are formed by interaction of CO2 with Zr3+ centers and hole states (OS-*), respectively. Mechanistic implications are discussed.     

Nonlinear Unmixing of Hyperspectral Datasets for the Study of Painted Works of Art

Nonlinear unmixing of hyperspectral reflectance data is one of the key problems in quantitative imaging of painted works of art. The approach presented is to interrogate a hyperspectral image cube by first decomposing it into a set of reflectance curves representing pure basis pigments and second to estimate the scattering and absorption coefficients of each pigment in a given pixel to produce estimates of the component fractions. This two‐step algorithm uses a deep neural network to qualitatively identify the constituent pigments in any unknown spectrum and, based on the pigment(s) present and Kubelka–Munk theory to estimate the pigment concentration on a per‐pixel basis. Using hyperspectral data acquired on a set of mock‐up paintings and a well‐characterized illuminated folio from the 15th century, the performance of the proposed algorithm is demonstrated for pigment recognition and quantitative estimation of concentration.     

Mechanistic studies of the formation of different states of oxygen on irradiated ZrO2 and the photocatalytic nature of photoprocesses from determination of turnover numbers

The photoadsorption of oxygen (photoreduction on electron surface-active centers) and the photoadsorption of hydrogen (photooxidation on hole surface-active centers) as well as the photooxidation of hydrogen in the presence of oxygen were examined over irradiated zirconia (ZrO2) specimens by thermoprogrammed desorption spectroscopy (TPD) and kinetically to assess the states (forms) of oxygen species formed on the surface of zirconia. The three TPD spectral maxima observed inferred three oxygen species of varying activity in the photooxidation of hydrogen. The number of surface-active sites on the zirconia surface were quantitatively estimated (ca. 1 x 10(16) centers), thereby permitting an estimate of the turnover numbers (TON) for the photooxidation of hydrogen (TON > 14.5) and for the photoreduction of oxygen (TON > 6.6). These demonstrate for the first time that a photoreaction occurring on the surface of a metal-oxide photocatalyst is truly photocatalytic.     

Acoustic streaming measurements in standing wave resonator using Particle Image Velocimetry

This paper experimentally investigates the measurement of acoustic streaming in a 7 m long-standing wave air-filled acoustic resonator. One can describe the acoustic streaming as a second-order steady flow, which is superimposed on the dominant acoustic velocity. It is induced by the nonlinearities of the acoustic propagation inside the resonator. The exploration of the acoustic velocity field by the synchronized PIV (stands for Particle Image Velocimetry) technique enabled to highlight and quantify these secondary flows. The PIV measurements of the acoustic velocity fields at different phases over the excitation signal period gave information on streaming profiles and the post processing applied allowed plotting the acoustic velocity over time. These results were compared to the outcome of a 2D numerical study performed with the commercial software Fluent, where good agreements were found. It indicates the ability of this method to accurately measure second order steady flow variations of the acoustic velocity field.     

Image stack alignment in full‐field X‐ray absorption spectroscopy using SIFT_PyOCL

Full‐field X‐ray absorption spectroscopy experiments allow the acquisition of millions of spectra within minutes. However, the construction of the hyperspectral image requires an image alignment procedure with sub‐pixel precision. While the image correlation algorithm has originally been used for image re‐alignment using translations, the Scale Invariant Feature Transform (SIFT) algorithm (which is by design robust versus rotation, illumination change, translation and scaling) presents an additional advantage: the alignment can be limited to a region of interest of any arbitrary shape. In this context, a Python module, named SIFT_PyOCL, has been developed. It implements a parallel version of the SIFT algorithm in OpenCL, providing high‐speed image registration and alignment both on processors and graphics cards. The performance of the algorithm allows online processing of large datasets.