Optical properties of zirconium oxynitride films: the effect of composition, electronic and crystalline structures

tThis work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied opticalresponses prompted by the variations in their compositional and structural properties. The films wereprepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2+ O2(17:3).The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gasflows to red-brownish for intermediate gas flows. Associated to this colour change there was a significantdecrease of brightness. With further increase of the reactive gas flow, the colour of the samples changedfrom red-brownish to dark blue or even to interference colourations. The variations in composition dis-closed the existence of four different zones, which were found to be closely related with the variationsin the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirco-nium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallizedover-stoichiometric nitride phase, which may be similar to that of Zr3N4with some probable oxygeninclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For highreactive gas flows, the films developed an oxynitride-type phase, similar to that of -Zr2ON2with someoxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2monoclinic type structurewithin the zone where films were prepared with relatively high reactive gas flows. The analysis carriedout by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of thed-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV.The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness anda colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to thesechanges, there was also a shift of the reflectivity minimum to lower energies, with the increase of thenon-metallic content. The samples lying in the two last zones (zone III, oxynitride and zone IV, oxide films)revealed a typical semi-transparent-optical behaviour showing interference-like colourations only dueto the complete depopulation of the d band at the Fermi level. The samples lying in these zones presentedalso an increase of the optical bandgap from 2 to 3.6 eV.

Thermo-compression molding of chitosan with a deep eutectic mixture for biofilms development

Supplementary information available at: http://www.rsc.org/suppdata/c5/gc/c5gc02231b/c5gc02231b1.pdf

Earthwork optimization system for sustainable highway construction

In highway construction, earthworks refer to the tasks of excavation, transportation, spreading and compaction of geomaterial (e.g. soil, rockfill and soil-rockfill mixture). Whereas relying heavily on machinery and repetitive processes, these tasks are highly susceptible to optimization. In this context Artificial Intelligent techniques, such as Data Mining and modern optimization can be applied for earthworks. A survey of these applications shows that they focus on the optimization of specific objectives and/or construction phases being possible to identify the capabilities and limitations of the analyzed techniques. Thus, according to the pinpointed drawbacks of these techniques, this paper describes a novel intelligent earthwork optimization system, capable of integrating DM, modern optimization and GIS technologies in order to optimize the earthwork processes throughout all phases of design and construction work. This integration system allows significant savings in time, cost and gas emissions contributing for a more sustainable construction.

Short-term corneal changes with gas-permeable contact lens wear in keratoconus subjects: a comparison of two fitting approaches

Purpose: To evaluate changes in anterior corneal topography and higher-order aberrations (HOA) after 14-days of rigid gas-permeable (RGP) contact lens (CL) wear in keratoconus subjects comparing two different fitting approaches. Methods: Thirty-one keratoconus subjects (50 eyes) without previous history of CL wear were recruited for the study. Subjects were randomly fitted to either an apical-touch or three-pointtouch fitting approach. The lens’ back optic zone radius (BOZR) was 0.4 mm and 0.1 mm flatter than the first definite apical clearance lens, respectively. Differences between the baseline and post-CL wear for steepest, flattest and average corneal power (ACP) readings, central corneal astigmatism (CCA), maximum tangential curvature (KTag), anterior corneal surface asphericity, anterior corneal surface HOA and thinnest corneal thickness measured with Pentacam were compared. Results: A statistically significant flattening was found over time on the flattest and steepest simulated keratometry and ACP in apical-touch group (all p < 0.01). A statistically significant reduction in KTag was found in both groups after contact lens wear (all p < 0.05). Significant reduction was found over time in CCA (p = 0.001) and anterior corneal asphericity in both groups (p < 0.001). Thickness at the thinnest corneal point increased significantly after CL wear (p < 0.0001). Coma-like and total HOA root mean square (RMS) error were significantly reduced following CL wearing in both fitting approaches (all p < 0.05). Conclusion: Short-term rigid gas-permeable CL wear flattens the anterior cornea, increases the thinnest corneal thickness and reduces anterior surface HOA in keratoconus subjects. Apicaltouch was associated with greater corneal flattening in comparison to three-point-touch lens wear.

Efficacy of a gas permeable contact lens to induce peripheral myopic defocus

Purpose. The purpose of this work was to evaluate the potential of a novel custom-designed rigid gas permeable (RGP) contact lens to modify the relative peripheral refractive error in a sample of myopic patients. Methods. Fifty-two right eyes of 52 myopic patients (mean [TSD] age, 21 [T2] years) with spherical refractive errors ranging from j0.75 to j8.00 diopters (D) and refractive astigmatism of 1.00 D or less were fitted with a novel experimental RGP (ExpRGP) lens designed to create myopic defocus in the peripheral retina. A standard RGP (StdRGP) lens was used as a control in the same eye. The relative peripheral refractive error was measured without the lens and with each of two lenses (StdRGP and ExpRGP) using an open-field autorefractometer from 30 degrees nasal to 30 degrees temporal, in 5-degree steps. The effectiveness of the lens design was evaluated as the amount of relative peripheral refractive error difference induced by the ExpRGP compared with no lens and with StdRGP conditions at 30 degrees in the nasal and temporal (averaged) peripheral visual fields. Results. Experimental RGP lens induced a significant change in relative peripheral refractive error compared with the nolens condition (baseline), beyond the 10 degrees of eccentricity to the nasal and temporal side of the visual field (p G 0.05). The maximum effect was achieved at 30 degrees. Wearing the ExpRGP lens, 60% of the eyes had peripheral myopia exceeding j1.00 D, whereas none of the eyes presented with this feature at baseline. There was no significant correlation (r = 0.04; p = 0.756) between the degree of myopia induced at 30 degrees of eccentricity of the visual field with the ExpRGP lens and the baseline refractive error. Conclusions. Custom-designed RGP contact lenses can generate a significant degree of relative peripheral myopia in myopic patients regardless of their baselin spherical equivalent refractive error.

Symptoms and signs in rigid gas permeable lens wearers during adaptation period

Objectives: To evaluate neophyte contact lens wearers’ fitting to rigid gas permeable (RGP) contact lenses in terms of wearing time, tear volume, stability, corneal staining, and subjective ratings, over a 1-month period of time. Methods: Twenty-two young healthy subjects were enrolled for wearing RGP on a daily wear basis. The participants included in this study never wore contact lenses and showed a value under 10 in McMonnies Questionnaire. Contact Lens Dry Eye Questionnaire, Visual Analog Scales, Schirmer test, tear film break-up time (BUT), and corneal staining grading were performed. Follow-up visits were scheduled at 1, 7, 15, and 28 days. Results: Six subjects dropped out due to discomfort from the study before 1 month (27% of discontinuation rate). Successful RGP wearers (16 participants) achieved high levels of subjective vision and reported comfort scores of approximately 9 of 10 between 10 and 15 days. They reported wearing their lenses for an average of 10.1262.43 hr after 1 month of wear. Conversely, unsuccessful wearers discontinued wearing the lenses after the first 10 to 15 days, showing comfort scores and wearing time significantly lower compared with the first day of wear. Schirmer test showed a signifi- cant increase at 10 days (P,0.001), and the BUT trends decreased after the first week of wear in unsuccessful group. Conclusions: Symptomatology related with dryness and discomfort, detected during the first 10 days of the adaptation, may help the clinician to predict those participants who will potentially fail to adapt to RGP lens wear.

Electrochromic devices incorporating biohybrid electrolytes doped with a lithium salt, an ionic liquid or a mixture of both

The sol-gel method was employed in the synthesis of di-urethane cross-linked poly( caprolactone) (PCL(530)/siloxane biohybrid ormolytes incorporating either a mixture of lithium triflate (LiCF3SO3) and the ionic liquid (IL) 1-ethyl-3-methyl imidazolium tetrafluoroborate ([Emim]BF4), or solely with [Emim]BF4 or LiCF3SO3. The ormolyte doped with [Emim]BF4 is thermally more stable and exhibits higher ionic conductivity (4 x 10-4 and 2 x 10-3 S cm-1 at 36 and 98 ºC, respectively) than those containing the LiCF3SO3/[Emim]BF4 mixture or just LiCF3SO3. The three ormolytes were employed in the production of glass/ITO/ormolyte/WO3/ITO/glass electrochromic devices (ECDs) designated as ECD@Y with Y = Li-[Emim]BF4, [Emim]BF4 and Li. The three ECDs displayed fast switching speed (ca. 30 s). ECD@Li-[Emim]BF4 exhibited an electrochromic contrast of 18.4 % and an optical density change of 0.11 in the visible region, the coloration efficiency attained at 555 nm was 159 and 80.2 cm-2 C-1 in the “on” and “off” states, respectively, and the open circuit memory was 48 hours. In the “on” state the CIE 1931 color space coordinates were x = 0.29 and y = 0.30, corresponding to blue color.

Production of medium-chain fatty acids and higher alcohols by a synthetic co-culture grown on carbon monoxide or syngas

Synthesis gas, a mixture of CO, H2, and CO2, is a promising renewable feedstock for bio-based production of organic chemicals. Production of medium-chain fatty acids can be performed via chain elongation, utilizing acetate and ethanol as main substrates. Acetate and ethanol are main products of syngas fermentation by acetogens. Therefore, syngas can be indirectly used as a substrate for the chain elongation process.

Toxicity induced by a metal mixture (Cd, Pb and Zn) in the yeast Pichia kudriavzevii: The role of oxidative stress

The present work aims to contribute for the elucidation of the role of oxidative stress in the toxicity associated with the exposure of Pichia kudriavzevii to multi-metals (Cd, Pb and Zn). Cells of the non-conventional yeast P. kudriavzevii exposed for 6 h to the action of multi-metals accumulated intracellular reactive oxygen species (ROS), evaluated through the oxidation of the probe 2,7-dichlorodihydrofluorescein diacetate. A progressive loss of membrane integrity (monitored using propidium iodide) was observed in multi-metal-treated cells. The triggering of intracellular ROS accumulation preceded the loss of membrane integrity. These results suggest that the disruption of membrane integrity can be attributed to the oxidative stress. The exposure of yeast cells to single metal showed that, under the concentrations tested, Pb was the metal responsible for the induction of the oxidative stress. Yeast cells coexposed to an antioxidant (ascorbic acid) and multi-metals did not accumulate intracellular ROS, but loss proliferation capacity. Together, the data obtained indicated that intracellular ROS accumulation contributed to metal toxicity, namely for the disruption of membrane integrity of the yeast P. kudriavzevii. It was proposed that Pb toxicity (the metal responsible for the toxic symptoms under the conditions tested) result from the combination of an ionic mechanism and the intracellular ROS accumulation.

Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source

The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with 13C-labeled CH4 (13CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, 13C-labeled CO2 (13CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with 13CO2 production and no methanogenesis occurred, excluding TMO as a possible source for 13CO2 production from 13CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment.

On modified simple reacting spheres kinetic model for chemically reactive gases

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