Study of the effect of the substitution of Fe by Ti on the microstructure and the physical properties of the perovskite system La0.67Ca0.2Ba0.13Fe1-xTixO3 with x = 0 and 0.03 at low temperatures.

La0.67Ca0.2Ba0.13Fe1-xTixO3 samples (x = 0 and 0.03) were synthesized by the auto-combustion method. Analysis of XRD diffractograms revealed that these compounds crystallize in the cubic system with the space group Pm3̄m. The dielectric properties have been studied in the 102-106 frequency range and the 120-280 K temperature range. Analysis of AC conductivity shows that the conduction mechanisms are of polaronic origin and that they are co-dominated by the NSPT and OLPT models. The monotonic increase in conductivity with increasing temperature results from the reduction of defect centers and the increase in charge carrier mobility. Such variation is consistent with impedance variation at different frequencies and temperatures indicating semiconductor behavior. Nyquist diagrams are characterized by the appearance of semi-circular arcs. These spectra are modeled in terms of equivalent electrical circuits confirming the contribution of grains (Rg//CPEg) and grain boundaries (Rgb//CPEgb). The dielectric analysis showed an evolution of the dielectric constant in accordance with Koop's theory and the phenomenological model of Maxwell-Wagner. The low conductivity and the high values of the real permittivity at low frequency make our compounds potential candidates for energy storage and applications for electronic devices and microwaves.

Research on the physical properties of LiMn0.5Fe2O4 spinel ferrites by the combination of optical, magnetic, and dielectric behaviors.

Ferrite compounds have recently attracted significant interest because of their multifunctional properties. This work investigates the optical, magnetic, and dielectric properties of a LiMn0.5Fe2O4 ferrite prepared by a solid-state reaction. Raman spectroscopy analysis substantiated the presence of the 5 active modes representing the vibration of the oxygen anion at both tetrahedral and octahedral sites. The direct optical band gap was estimated to be 3.51 eV, which indicates the semiconductor behavior of the compound. A theoretical modulation of the hysteresis loop was done to confirm the dominance of the ferromagnetic contribution over the antiferromagnetic one. Furthermore, the dielectric permittivity result indicated a colossal value of the order of 103. The dielectric losses are characterized by the Giuntini law to extract the relaxation process, which is hidden by the DC-conductivity process. Our results indicate the potential of LiMn0.5Fe2O4 for applications in multifunctional devices.

Investigation of temperature and frequency dependence of the dielectric properties of multiferroic (La0.8Ca0.2)0.4Bi0.6FeO3 nanoparticles for energy storage application.

In this work we synthesized the multifunctional (La0.8Ca0.2)0.4Bi0.6FeO3 material using a sol-gel process. Structural and morphologic investigations reveal a Pnma perovskite structure at room temperature with spherical and polygonal nanoparticles. A detailed study of the temperature dependence of the dielectric and electrical properties of the studied material proves a typical FE-PE transition with a colossal value of real permittivity at 350 K that allows the use of this material in energy storage devices. Thus, the investigation of the frequency dependence of the ac conductivity proves a correlated barrier hopping (CBH) conduction mechanism to be dominant in the temperature ranges of 150-170 K; the two observed Jonscher's power law exponents, s 1 and s 2 between 180 K and 270 K correspond to the observed dispersions in the ac conductivity spectra in this temperature region, unlike in the temperature range of 250-320 K, the small polaron tunnel (NSPT) was considered the appropriate conduction model.

Structural, morphological, Raman, dielectric and electrical properties of La1-2x Ba x Bi x FeO3 (0.00 ≤ x ≤ 0.20) compounds.

La1-2x Ba x Bi x FeO3 (0.00 ≤ x ≤ 0.20) nanoparticles were prepared by the auto-combustion method using glycine as a combustion fuel. X-ray diffractometry (XRD) measurements confirmed the orthorhombic structure of the synthesized compounds with the Pnma space group as a principal majority phase and showed the presence of a very minor secondary phase when x > 0.1. The nanosize criterion of the prepared compounds was confirmed from the crystallite size values calculated using the Williamson-Hall formalism. The relaxation process has been studied by the frequency dependence of the imaginary parts of impedance and modulus (Z'' and M'') which satisfied the Arrhenius law. Nyquist plots allowed us to obtain an adequate equivalent circuit involving the grains and grain boundary contributions. The activation energies calculated from Z'', M'' and the resistance of both contributions deduced from the Nyquist plots are found to be very similar. The conduction mechanism has been analyzed using the temperature dependence of the exponent Jonscher's power law parameter which confirms the NSPT conduction mechanism type for all compounds with an enhancement of the binding energy of the charge carrier (W H) with the substitution.

Study of the influence of 2.5% Mg2+ insertion in the B-site of La0.8Ca0.1Pb0.1FeO3 on its structural, electrical and dielectric properties.

This work involves the synthesis and study of physical properties of the La0.8Ca0.1Pb0.1Fe0.975Mg0.025O3 compound, which has been characterized by various experimental techniques, such as X-ray diffraction, SEM and complex impedance spectroscopy. The structural study showed that the La0.8Ca0.1Pb0.1Fe0.975Mg0.025O3 compound crystallized in the orthorhombic structure with the Pnma space group. The particle size and the surface morphology of this compound have been analysed using SEM. The particle size was found to be around 120 nm and we confirmed that one particle contains more than one crystallite. Importantly, the studied compound presented a giant dielectric permittivity (ε' of around 9 × 104 at high temperature and low frequencies). An equivalent electric circuit has been deduced from the Nyquist plots of the complex impedance parts (Z'' vs. Z') to correctly describe the electrical behavior of the La0.8Ca0.1Pb0.1Fe0.975Mg0.025O3 compound. The chosen circuit consists of two cells mounted in series corresponding to the grain and grain boundary contributions. The electrode contribution has been detected from the frequency dependence of the imaginary part of modulus where the activation energy of each constitution has been calculated. The relaxation process and the electrical conductivity are attributed to the same type of charge carriers characterized by similar values of the activation energy determined from loss factor tangent (tg(δ)), the imaginary part of the permittivity and the modulus spectrum.

Electrical conductivity and dielectric properties of Sr doped M-type barium hexaferrite BaFe12O19.

The hexaferrite Ba1-x Sr x Fe12O19 compounds with x = 0, 0.5 and 1 were synthesized by the autocombustion method. X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM) were used for structural and morphological studies.

Photosensitive activity of fabricated core-shell composite nanostructured p-CuO@CuS/n-Si diode for photodetection applications.

Development of photo detectors based on different semiconducting materials with high performance has been in progress in recent past, however, there is a lot of difficulties in developing the more effective photo detectors-based devices with high responsivity, detectivity and quantum efficiency. Hence, we have synthesized pure CuS and CuO@CuS core-shell heterostructure based photo detectors with high performance by simple and cost-effective two-step chemical co-precipitation method. The phase purity of CuS and CuO@CuS composite was observed by XRD analysis and the result were verified with Raman spectroscopy studies. Sphere like morphology of pure CuS and core-shell structure formation of CuO@CuS are observed with scanning and transmission electron microscopes. The presence of expected elements has been confirmed with EDX elemental mapping. Light harvesting photodiodes were fabricated by using n-type silicon substrate through drop cost method. Photo sensitive parameters of fabricated diodes were analyzed by I-V characteristics. The p-CuO@CuS (1:1)/n-Si diode owned a maximum photosensitivity (Ps) ∼ 7.76 × 104 %, photoresponsivity (R) ∼ 798.61 mA/W, external quantum efficiency ( E Q E )∼309.66 % and specific detectivity (D*) ∼ 8.19 × 1011 Jones when compared to p-CuS/n-Si diode. The obtained results revealed that the core/shell heterostructure of CuO@CuS is the most appropriate for photo detection.

Effect of Bi-substitution into the A-site of multiferroic La0.8Ca0.2FeO3 on structural, electrical and dielectric properties.

(La0.8Ca0.2)1-x Bi x FeO3 (x = 0.00, 0.05, 0.10, 0.15 and 0.20) (LCBFO) multiferroic compounds have been prepared by the sol-gel method and calcined at 800 °C. X-ray diffraction results have shown that all samples crystallise in the orthorhombic structure with the Pnma space group. Electrical and dielectric characterizations of the synthesized materials have been performed using complex impedance spectroscopy techniques in the frequency range from 100 Hz to 1 MHz and in a temperature range from 170 to 300 K. The ac-conductivity spectra have been analysed using Jonscher's power law σ(ω) = σ dc + Aω s , where the power law exponent (s) increases with the temperature. The imaginary part of the complex impedance (Z'') was found to be frequency dependent and shows relaxation peaks that move towards higher frequencies with the increase of the temperature. The relaxation activation energy deduced from the Z'' vs. frequency plots was similar to the conduction activation energy obtained from the conductivity. Hence, the relaxation process and the conduction mechanism may be attributed to the same type of charge carriers. The Nyquist plots (Z'' vs. Z') at different temperatures revealed the appearance of two semi-circular arcs corresponding to grain and grain boundary contributions.

Structural study and large magnetocaloric entropy change at room temperature of La1-x □ x MnO3 compounds.

In this study, our central focus is to investigate the magnetocaloric characteristics of a La1-x □ x MnO3 (x = 0.1, 0.2 and 0.3) series prepared by a sol-gel technique published in Prog. Mater. Sci., 93, 2018, 112-232. The crystallographic study revealed that our compounds crystallize in a rhombohedral structure with R3̄c. Ferromagnetic (FM) and paramagnetic (PM) characters were detected from the variation in magnetization as a function of magnetic fields at different temperatures. The second order transition was verified from the Arrott plots (M 2 vs. (µ 0 H/M)), where the slopes have a positive value. In order to verify the second order, we traced the variation of magnetization vs. temperature at different magnetic fields for x = 0.2. This revealed a ferromagnetic (FM)-paramagnetic (PM) transition when temperature increases. Relying on the indirect method while using the Maxwell formula, we determined the variation in the entropy (-ΔS M) as a function of temperature for different magnetic fields for the three samples. We note that all the studied systems stand as good candidates for magnetic refrigeration with relative cooling power (RCP) values of around 131.4, 83.38 and 57.26 J kg-1 with magnetic fields below 2 T, respectively. Subsequently, the magnetocaloric effect was investigated by a phenomenological model for x = 0.2. The extracted data confirm that this phenomenological model is appropriate for the prediction of magnetocaloric properties. The study also demonstrated that this La0.8□0.2MnO3 system exhibits a universal behaviour.

Multicaloric effect in a multiferroic composite of Gd5(Si,Ge)4 microparticles embedded into a ferroelectric PVDF matrix.

The coupling between electric, magnetic and elastic features in multiferroic materials is an emerging field in materials science, with important applications on alternative solid-state cooling technologies, energy harvesting and sensors/actuators. In this direction, we developed a thorough investigation of a multiferroic composite, comprising magnetocaloric/magnetostrictive Gd[Formula: see text]Si[Formula: see text]Ge[Formula: see text] microparticles blended into a piezo- and pyroelectric poly(vinylidene) fluoride (PVDF) matrix. Using a simple solvent casting technique, the formation and stabilization of PVDF electroactive phases are improved when the filler content increases from 2 to 12 weight fraction (wt.%). This effect greatly contributes to the magnetoelectric (ME) coupling, with the ME coefficient [Formula: see text] increasing from 0.3 V/cm.Oe to 2.2 V/cm.Oe, by increasing the amount of magnetic material. In addition, magnetic measurements revealed that the ME-coupling has influenced the magnetocaloric effect via a contribution from the electroactive polymer and hence leading to a multicaloric effect. These results contribute to the development of multifunctional systems for novel technologies.

The growth and improved magnetoelectric response of strain-modified Aurivillius SrBi4.25La0.75Ti4FeO18 thin films.

In this study, we grew 5-layered SrBi4.25La0.75Ti4FeO18 (SBLFT) polycrystalline thin films (80-330 nm thick) via pulsed-laser deposition to study their ferroelectric and magnetoelectric response. Structural/microstructural analysis confirmed the formation of orthorhombic SBLFT with good crystallinity and randomly oriented Aurivillius phases. Detailed scanning transmission electron microscopy analysis of 120 nm film revealed a predominantly five-layered structure with the coexistence of four-layer stacking. Such stacking defects are found to be pertinent to the high structural flexibility of Bi-rich Aurivillius phases, alleviated by lattice strain. Raman spectral features at ambient temperatures depict the signature of the orthorhombic-tetragonal phase transition. SBLFT films have a strong ferroelectric nature (remanent polarization 2Pr of 35 µC cm-2) with a fatigue endurance up to 1010 cycles and strongly improved, switchable magnetization as opposed to its antiferromagnetic bulk counterpart. The scaling behavior of dynamic hysteresis reveals that ferroelectric domain reversal has good stability and low energy consumption. We observed the presence of SBLFT nanoregions (1-5 nm), distributed across the film, with Bi and Fe-rich compositions and oxygen vacancies that contribute to the weak ferromagnetic behavior mediated by the Dzyaloshinskii-Moriya interactions. Subtle changes in the structural strain and lattice distortions of thin films with varied thicknesses led to distinct ferroic properties. Stronger ferroelectric polarization of 80 nm and 120 nm films compared to that of thicker ones can be due to structural strain and the possible rearrangement of BO6 octahedra. The observation of the improved magnetoelectric coefficient of 50 mV cm-1 Oe-1 for 120 nm film, as compared to that of several Aurivillius oxides, indicates that the structural strain modification in SBLFT is beneficial for the fatigue-free magnetic field switching of ferroelectric polarization. The structural strain of the unit cell as well as the presence of Bi- and ferromagnetic Fe-rich nanoregions was found to be responsible for the improved multiferroic behaviour of the SBLFT films.

The relationship between mesorectal grading and oncological outcome in rectal adenocarcinoma.

AIM: The prognostic association between mesorectal grading and oncological outcome in patients undergoing resection for rectal adenocarcinoma is controversial. The aim of this retrospective chart review was to determine the individual impact of mesorectal grading on rectal cancer outcomes. METHOD: We compared oncological outcomes in patients with complete, near-complete and incomplete mesorectum who underwent rectal excision with curative intent from 2009 to 2014 for Stage cI-III rectal adenocarcinoma. We also assessed the independent association of mesorectal grading and oncological outcome using multivariate models including other relevant variables. RESULTS: Out of 505 patients (339 men, median age of 60 years), 347 (69%) underwent a restorative procedure. There were 452 (89.5%), 33 (6.5%) and 20 (4%) patients with a complete, near-complete and incomplete mesorectum, respectively. Local recurrence was seen in 2.4% (n = 12) patients after a mean follow-up of 3.1 ± 1.7 years. Unadjusted 3-year Kaplan-Meier analysis by mesorectal grade showed decreased rates of overall, disease-free and cancer-specific survival and increased rates of overall and distant recurrence with a near-complete mesorectum, while local recurrence was increased in cases of an incomplete mesorectum (all P < 0.05). On multivariate analyses, a near-complete mesorectum was independently associated with decreased cancer-specific survival (hazard ratio 0.26, 95% CI 0.1-0.7; P = 0.007). There were no associations between mesorectal grading and overall survival, disease-free survival, overall recurrence or distant recurrence (all P > 0.05). CONCLUSION: Mesorectal grading is independently associated with oncological outcome. It provides unique information for optimizing surgical quality in rectal cancer.

Unusual redox behaviour of the magnetite/hematite core-shell structures processed by the laser floating zone method.

Magnetite (Fe3O4) offers unique physical and chemical properties, being an important material for many industrial applications. Certain limitations on the application conditions are, however, imposed by the redox stability issue. Fine control of the iron oxidation states represents a challenge for materials engineering. The present work explores relevant redox processes in iron oxides, processed under highly non-equilibrium laser floating zone (LFZ) conditions under atmospheres with different oxygen activities. The as-grown fibres showed a structure composed of the Fe3O4 core and the Fe2O3 shell. This study uncovers unexpectedly lower hematite content and shell thickness for the fibres processed under more oxidizing conditions. Combined structural and microstructural studies, supported by the analysis of the existing literature data, strongly suggest that the redox processes during the LFZ process can be rather determined by kinetics of melt crystallization, nuclei formation and heat transfer than by the oxygen content in the gas phase. The proposed mechanisms are further confirmed by electrical and magnetic studies of the composite fibres.

Factors affecting the fate of faecal diversion in patients with perianal Crohn's disease.

AIM: A study was carried out with the aim of identifying potential factors which might influence the fate of patients undergoing faecal diversion by stoma in perianal Crohn's disease. METHOD: Patients with severe perianal Crohn's disease undergoing faecal diversion between 1994 and 2012 were identified and the factors associated with stoma closure were assessed using univariate and multivariate analysis. RESULTS: Of 138 diverted patients, 30 (22%) achieved stoma closure, 45 (33%) had a stoma with the rectum left in situ and 63 (45%) underwent proctectomy with permanent stoma formation after a mean follow-up of 5.7 years. Univariate analysis demonstrated that synchronous colonic (P = 0.004) or rectal (P = 0.021) disease involvement and an increased frequency of loose seton placement (P = 0.001) adversely affected successful stoma closure rates. Multivariate analysis indicated a significant association between the inability to achieve stoma closure and persisting rectal involvement (OR 7.5, 95% CI 2.4-33.4), one or two placements of a loose seton (OR 3.3, 95% CI 1.4-8.8) and more than two placements (OR 6.9, 95% CI 1.2-132.5). No specific medical management was associated with an improved stoma closure rate, including biological agents when these were available (P = 0.25). CONCLUSION: The fate of temporary faecal diversion in patients with perianal Crohn's disease is adversely affected by aggressive disease characteristics. No particular treatment, including biological therapy, was associated with an improved outcome.

Observation of magnetoelectric coupling and local piezoresponse in modified (Na0.5Bi0.5)TiO3-BaTiO3-CoFe2O4 lead-free composites.

Lead-free particulate multiferroic composites of [0.94(Na0.5Bi0.5)TiO3-0.06 BaTiO3]:(Co0.6Zn0.4)(Fe1.7Mn0.3)O4 were synthesized and magnetoelectric (ME) properties were studied. X-ray diffraction and microstructural studies indicated the formation of a two-phase composite system without any impurities. The shift of Raman modes corresponding to ferroelectric and ferrite phases was assigned to the induced strain amid the formation of a two-phase system, in relation to the fraction of each phase in the samples. A strong local piezoresponse and hysteresis loops observed for composites established the ferroelectric properties at a nanoscale. Magnetostriction measurements revealed values of λ11 = -10.4 and λ12 = 5.3 ppm and piezomagnetic coefficient dλ11/dH = -0.0087 ppm Oe(-1) at 0.45 kOe for a composite with a ferrite concentration of 35 mol%. A maximum change of 18.5% in magnetization after electrical poling indicates a strong magnetoelectric response of the present composites followed by a direct ME coefficient of 8.2 mV cm(-1) Oe(-1). Our studies point to the fact that the present multiferroic composites having strong ME coupling are useful for lead-free electronic applications.

Layered surgical repair of traumatic cloacal deformities: technical details and functional outcomes.

BACKGROUND: Traumatic cloaca due to severe obstetric injury is a disabling condition that results in debilitating fecal incontinence, sexual dysfunction, and psychosocial distress for the patients, and poses a complex and challenging clinical situation for the surgeon. The aim of this study is to describe our technique and functional outcomes for the surgical repair of traumatic cloacal deformities. METHODS: Between 2000 and 2010, four women with traumatic cloacal deformities related to obstetric injury underwent repair by a single surgeon. In all patients, a systematic layered repair of the anovaginal structures was performed, including internal and external sphincteroplasties, without the implementation of tissue flaps or fecal diversion. Anorectal function before and after surgery as well as wound healing was evaluated. The patients presented 4.8 years after the obstetric injury. Mean preoperative Fecal Incontinence Severity Index was 34. All patients had complete disruption of the perineum, anal canal, distal vagina, and rectum, with a mean external sphincter defect of 151 degrees. RESULTS: Postoperatively, there were no wound-related complications and complete healing occurred by the fourth week. Median long-term follow-up was 4.5 years. At long-term follow-up, mean postoperative Fecal Incontinence Severity Index score was zero and all patients reported complete absence of dyspareunia. CONCLUSIONS: A layered surgical repair of cloacal deformities after severe obstetrical injury is associated with excellent functional outcomes and cosmetic results. The need for fecal diversion or complex surgical flaps for wound closure is obviated in this small series.

Study of the optical and dielectric properties of TiO2 nanocrystals prepared by the Pechini method.

Titanium oxide nanocrystals synthesized by the Pechini method were calcinated at temperatures between 300 and 1000 degrees C. The crystalline structure was analysed by X-ray diffraction, scanning electron microscopy (SEM) and Raman spectroscopy. A phase transition from the anatase to rutile crystalline phase was found to occur at temperatures near 500 degrees C. The samples were characterized by photoluminescence (PL) and dielectric spectroscopy. The influence of the calcination temperature on the visible and near infrared luminescence is discussed. A correlation between the structural properties, luminescence and dielectric properties are discussed.

The impact of the summer 2003 heat wave in Iberia: how should we measure it?

We present a new approach to improve the reliability of quantifying the impact of a heat wave on mortality rates. We show, for the recent European summer 2003 heat wave, that the use of absolute maximum temperature values, or number of days above a given threshold, can be misleading. Here, we have assessed the impact of the heat wave on Iberian mortality by applying a four step procedure: (1) calculating, for each observatory, the local maximum temperature (T (max)) distributions, (2) calculating the corresponding 95th percentile values (T (threshold)), (3) locally defining extremely hot days (EHD) as those days on which the local threshold of the 95th percentile of the series is exceeded, and (4) calculating the total degrees-days (DD) of exceedance, by calculating the difference T (max)-T (threshold) and summing these values for all days above T (threshold). We show that the relationship between summer mortality rates and the DD index is non-linear and can be described by a logarithmic function, with a correlation coefficient of 0.78, which explains 60.6% of the mortality variance (F value of 24.64, significant at P<0.0001). Using maximum temperatures, no significant relationship is found with mortality, whereas the EHD frequency shows a significant association with mortality, albeit weaker than that obtained with DD.