Isostructural second-order phase transition of b-Bi2O3 at high pressures: an experimental and theoretical study

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp507826jWe report a joint experimental and theoretical study of the structural and vibrational properties of synthetic sphaerobismoite (beta-Bi2O3) at high pressures in which room-temperature angle-dispersive X-ray diffraction (XRD) and Raman scattering measurements have been complemented with ab initio total energy and lattice dynamics calculations. Striking changes in Raman spectra were observed around 2 GPa, whereas X-ray diffraction measurements evidence no change in the tetragonal symmetry of the compound up to 20 GPa; however, a significant change exists in the compressibility when increasing pressure above 2 GPa. These features have been understood by means of theoretical calculations, which show that beta-Bi2O3 undergoes a pressure-induced isostructural phase transition near 2 GPa. In the new isostructural beta' phase, the Bi3+ and O2- environments become more regular than those in the original beta phase because of the strong decrease in the activity of the lone electron pair of Bi above 2 GPa. Raman measurements and theoretical calculations provide evidence of the second-order nature of the pressure-induced isostructural transition. Above 20 GPa, XRD measurements suggest a partial amorphization of the sample despite Raman measurements still show weak peaks, probably related to a new unknown phase which remains up to 27 GPa. On pressure release, XRD patterns and Raman spectra below 2 GPa correspond to elemental Bi-I, thus evidencing a pressure-induced decomposition of the sample during downstroke.Financial support from the Spanish Consolider Ingenio 2010 Program (MALTA Project CSD2007-00045) is acknowledged. This work was also supported by Brazilian Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) under Project 201050/2012-9, Spanish MICINN under Projects MAT2010-21270-004-01/03/04 and MAT2013-46649-C4-2/3/4-P, Spanish MINECO under Project CTQ2012-36253-C03-02, and from Vicerrectorado de Investigacion de la Universitat Politecnica de Valencia under Projects UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. JAS. acknowledges Juan de la Cierva fellowship program for financial support.Pereira, ALJ.; Sans Tresserras, JÁ.; Vilaplana Cerda, RI.; Gomis, O.; Manjón Herrera, FJ.; Rodriguez-Hernandez, P.; Muñoz, A.... (2014). Isostructural second-order phase transition of b-Bi2O3 at high pressures: an experimental and theoretical study. Journal of Physical Chemistry C. 118(40):23189-23201. https://doi.org/10.1021/jp507826jS23189232011184

Burnout among surgeons before and during the SARS-CoV-2 pandemic: an international survey

Background: SARS-CoV-2 pandemic has had many significant impacts within the surgical realm, and surgeons have been obligated to reconsider almost every aspect of daily clinical practice. Methods: This is a cross-sectional study reported in compliance with the CHERRIES guidelines and conducted through an online platform from June 14th to July 15th, 2020. The primary outcome was the burden of burnout during the pandemic indicated by the validated Shirom-Melamed Burnout Measure. Results: Nine hundred fifty-four surgeons completed the survey. The median length of practice was 10 years; 78.2% included were male with a median age of 37 years old, 39.5% were consultants, 68.9% were general surgeons, and 55.7% were affiliated with an academic institution. Overall, there was a significant increase in the mean burnout score during the pandemic; longer years of practice and older age were significantly associated with less burnout. There were significant reductions in the median number of outpatient visits, operated cases, on-call hours, emergency visits, and research work, so, 48.2% of respondents felt that the training resources were insufficient. The majority (81.3%) of respondents reported that their hospitals were included in the management of COVID-19, 66.5% felt their roles had been minimized; 41% were asked to assist in non-surgical medical practices, and 37.6% of respondents were included in COVID-19 management. Conclusions: There was a significant burnout among trainees. Almost all aspects of clinical and research activities were affected with a significant reduction in the volume of research, outpatient clinic visits, surgical procedures, on-call hours, and emergency cases hindering the training. Trial registration: The study was registered on clicaltrials.gov "NCT04433286" on 16/06/2020

The effects of delayed annealing on the luminescent activity of heavy metal cadmium zinc phosphate glasses activated by: Er3+ and Tb3+ ions

Abstract The luminescent spectra of the RE2O3-doped P2O5–CdO–ZnO glasses (RE = Er, and Tb) were investigated to separate the effects of two studied rare-earth elements and the annealing regime on the emission performance of the prepared glasses. The glasses undergo a series of collective measurements including UV–visible absorption, luminescence, thermal expansion, XRD, TEM, and FTIR. The optical UV–visible spectra of the two doped glasses reveal a UV band due to undoped glass beside and extra extended 11 peaks with the Er3+ ions with high distinct features while the Tb3+ ions samples exhibit peaks within the visible region. These peaks are correlated with transitions from the ground state in each case to specific energy transitions. The overall optical data indicate that the two rare earth ions are present in a stable trivalent state. Under UV excitation, both Er3+ and Tb3+ emit a characteristic green light corresponding to 4S3/2 → 4I15/2 and 5D4 → 7F5 transitions, respectively. The performance of the green light was identified to be enhanced by increasing the concentration of rare earth and the effect of annealing temperature. Moreover, the intensity of the infrared emission of Er3+ at 1532 nm corresponds to the (4I13/2 → 4I15/2) transition which is assumed to be developed with the effect of heating. The resultant IR spectra show distinct vibrational peaks due to phosphate groups that undergo only minor modifications when doped with rare earth elements or over-annealed

Zinc containing borate glasses and glass-ceramics: Search for biomedical applications

Ternary soda lime borate glass and samples with ZnO replacing CaO up to 10 mol% were prepared and studied for their bone bonding ability. Fourier transform infrared (FTIR) absorption spectra of the prepared glasses before and after immersion in simulated body fluid (SBF), for one or two weeks, showed the appearance of calcium phosphate (hydroxyapatite (HA)) which is an indication of bone bonding ability. X-ray diffraction patterns were measured for the glasses and indicated the presence of small peaks related to hydroxyapatite in the samples immersed in SBF. The glasses were heat treated with controlled two-step regime to convert them to their corresponding glass-ceramic derivatives. FTIR and X-ray diffraction measurements of the glass-ceramic samples (before and after immersion in SBF) confirmed the appearance of HA which is influenced by ZnO content. The overall data are explained on the basis of current views about the corrosion behaviour of borate glasses including hydrolysis and direct dissolution mechanism

Optical and infrared absorption of gamma irradiated ternary silicate glasses containing NiO

651-666<span style="font-size: 15.0pt;mso-bidi-font-size:8.0pt;font-family:" times="" new="" roman","serif""="">The optical and infrared absorption spectra of ternary silicate glasses containing NiO were studied systematically, as function of glass composition. The same properties were measured after successive gamma ray irradiation. The induced spectra and the rate of formation of the intrinsic defect of the base glass and the extrinsic detect due to the nickel ion were calculated. The experimental optical results were analysed and explained by assuming that, nickel exists in glass as divalent Ni ions in two different states of coordination, namely, octahedral and tetrahedral. The infrared spectra of the doped glasses reveal the same spectra of the undoped glasses retaining the main vibrational bands which indicate that the dopant oxide has no effect on the main structural building groups. The rates of formation and annihilation of the color centers produced by gamma irradiation are believed to approach saturation or equilibrium with prolonged irradiation. </span

Collective Optical, FTIR, and Photoluminescence Spectra of CeO2 and/or Sm2O3-Doped Na2O–ZnO–P2O5 Glasses

Glasses with the Na2O–ZnO–P2O5 composition and doped with single CeO2, Sm2O3, or mixed dopants were melted and studied. Collective optical, photoluminescence, and FT-infrared spectral studies were carried out. CeO2-doped glasses show two extra UV absorption bands due to Ce4+ and Ce3+ ions while Sm2O3-doped samples reveal pronounced peaks collected into two segments from 367 to 472 nm and from 950 to 1623 nm which are characteristic of absorption from Sm3+ ions. The mixed dopants glasses show combined UV-visible–near-IR absorption peaks due to cerium (Ce4+, Ce3+) ions and samarium (Sm3+) ions. The photoluminescence spectra (PL) of the single CeO2-doped and Sm2O3-doped glasses and even the mixed dopant sample reveal luminescence spectra after excitation which are characteristic of the rare-earth ions. The intensities for both excited or emitted peaks are found to increase with the increase of the rare-earth percent. FTIR spectra of the glasses show pronounced vibrational peaks related to phosphate groups (Q2 and Q3 units) in accordance with the P2O5 percent (70 mol %)

Characterization of bioactivity in transition metal doped-borosilicate glasses by infrared reflection and dielectric studies

880-888Borosilicate glasses with the addition of one of the 3d-transition metals (Ti→Cu) (0.1 g/100g glass) have been investigated as possible materials having bioactivity by infrared reflection spectroscopy and electrical properties after the immersion in simulated body fluid (SPF) for different interval of times. The results show obvious effects of the transition metal ions on the bioactivity of the borosilicate glasses. The results are discussed taking into consideration recent achievements that govern the formation of hydroxyapatite surface layer on glass. Also, IR and electrical results are discussed in relation to the glass composition and structure, which confirm the effect of the formation of HAp layer and the possible mixed ionic and electronic mechanisms due to the addition of transition metal oxides