Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Fabrication and frequency response of a complex ultrasonic transducer for multilayer evaluation

To characterize the thickness of a corrosive fluid system's coated facilities, such as pipes, tubes, tanks, and structural members, a complex ultrasonic transducer capable of measuring multilayered parts was fabricated and the time and frequency responses were evaluated. The target transducer was constructed with two active dual elements made from tape-cast PbNb₂O₆ sheets and an additional thin-film active element made from sol–gel spin-coated Pb(Zr_0.52Ti_0.48)O₃ films. After adjusting the properties of each active element, a complex transducer was assembled after matching the impedance of each element and considering the minimal interference between the active layers. The impulse response of the assembled complex transducer shows excellent characteristics. Moreover, the assembled transducer's capability of accurately measuring the thickness assures that it can be directly applied to related industries.     

Potential tissue implants from the networks based on 1,5-dioxepan-2-one and ε-caprolactone

The synthesis and characterization of degradable polymeric networks for biomedical applications was performed. Cross-linked films of poly(ε-caprolactone) (PCL) and poly(1,5-dioxepan-2-one) (PDXO) having various mole fractions of monomers and different cross-link densities were successfully prepared using 2,2′-bis-(ε-caprolactone-4-yl) propane (BCP) as cross-linking agent. Reaction parameters were carefully examined to optimise the film-forming conditions. Networks obtained were elastomeric materials, easy to cast and remove from the mould. Effect of CL content and cross-link density on the final properties of the polymer network was evaluated. High CL content or degree of cross-linking led to increase in Young's modulus and decrease in elongation at break. An increase in crystalline domains in films having a higher CL content was observed by optical microscopy. A greater thermal stability was observed in films having a high CL content. The hydrophilicity of the materials could be tailored by changing the CL content. The surface of the films became rougher with higher CL content.     

Highly ordered microstructures of poly(styrene-b-isoprene) block copolymers induced by solution meniscus

Microstructures of hundreds of micron thick poly(styrene-block-isoprene) copolymer films solution-cast in a cylindrical tube with the solvent evaporation controlled were investigated by transmission electron microscope (TEM), small angle X-ray scattering (SAXS) and optical microscope (OM). In a block copolymer with cylindrical polyisoprene microdomains, the orientation of the cylinders was varied along radial direction of the cylindrical tube. Highly aligned hexagonal arrays of in-plane polyisoprene cylinders were formed with their cylindrical axis parallel to the circumference of the tube in the regimes close to the wall edge. In contrast randomly ordered microdomains were observed at the center of the tube. We have also found that the orientation depends on the solvent evaporation rate and an intermediate rate (∼2.3 nL/s) provides the best orientation. In the case of a block copolymer with a bicontinuous double gyroid structure, we obtained a globally ordered microstructure where [111] crystallographic direction was parallel to the circumference of the tube. For both block copolymers, the area of highly ordered arrays of nanoscopic domains is over 1 mm². Development of the orientation was explained by coupling two orthogonal fields: (1) The flow of a solution induced by strong capillary force at a meniscus between the cylindrical tube wall and the block copolymer solution and (2) the solvent evaporation.     

Subcritical crack growth processes in SiC/SiC ceramic matrix composites

Ceramic matrix composites have the potential to operate at high temperatures and are, therefore being considered for a variety of advanced energy technologies such as combustor liners in land-based gas turbo/generators, heat exchangers and advanced fission and fusion reactors. Ceramic matrix composites exhibit a range of crack growth mechanisms driven by a range of environmental and nuclear conditions. The crack growth mechanisms include: (1) fiber relaxation by thermal (FR) and irradiation (FIR) processes, (2) fiber stress-rupture (SR), (3) interface removal (IR) by oxidation, and (4) oxidation embrittlement (OE) resulting from glass formation including effects of glass viscosity. Analysis of these crack growth processes has been accomplished with a combination experimental/modeling effort. Dynamic, high-temperature, in situ crack growth measurements have been made in variable Ar + O₂ environments while a Pacific Northwest National Laboratory (PNNL) developed model has been used to extrapolate this data and to add radiation effects. In addition to the modeling effort, a map showing these mechanisms as a function of environmental parameters was developed. This mechanism map is an effective tool for identifying operating regimes and predicting behavior. The process used to develop the crack growth mechanism map was to: (1) hypothesize and experimentally verify the operative mechanisms, (2) develop an analytical model for each mechanism, and (3) define the operating regime and boundary conditions for each mechanism. A map for SiC/SiC composites has been developed for chemical and nuclear environments as a function of temperature and time.     

Calculations of optical properties in p-doped nitrides quaternary alloys multiple quantum wells

We present theoretical photoluminescence (PL) and absorption spectra of p-doped InGaN/AlInGaN and AlInGaN/InGaN multiple quantum wells (MQWs). The calculations were performed within the k.p method by means of solving a full eight-band Kane Hamiltonian together with the Poisson equation in a plane wave representation, including exchange–correlation effects within the local density approximation. Strain effects due to the lattice mismatch and an internal electric field are also taken into account. We show that by changing the In and Al composition we can reach short and long emission wavelengths. The trends in the calculated Stokes shift, due to many-body effects within the quasi-two-dimensional hole gas (2DHG), are analyzed as a function of the acceptor doping concentration. Since the studies of optical properties of quantum wells based on nitrides quaternary alloys are at an early stage, the results reported here will provide guidelines for the interpretation of forthcoming experiments.     

Morphology/behaviour relationship of nanocomposites based on natural rubber/epoxidized natural rubber blends

In order to analyze the effect of an epoxidized natural rubber (ENR) and filler treatment on the morphology and behavior of natural rubber (NR) nanocomposites, blends of these polymers have been prepared. The nature and extent of the clay dispersions in the filled samples were evaluated by X-ray diffraction. In the presence of ENR, an exfoliated structure was obtained which suggests that enough rubbery polymer was incorporated into the interlayer spacing. The effect of clay in rubber compounds was analyzed through rheological, mechanical and swelling characterization. A sensible improvement in the nanocomposite properties was observed by the addition of organoclay. It has been deduced that the properties of the compounds strongly depend on the extent of the silicate nanolayers dispersion into the rubber matrices as well as on the organoclay type and elastomer compatibility.     

Single and multi-specimenR-curve methods forJ IC determination of toughened nylons

For characterization of the fracture resistance of materials used in the upper shelf toughness regime,J-R curves are widely considered the most promising candidates. However, there still remain problems concerning both the generation and measurement ofJ-R curves as material characterizing parameters and their application in ductile fracture analyses for failure prediction in polymeric materials. This paper reports the results of investigations conducted on two rubbertoughened nylons at room temperature. Two different methods ofJ-R curve determination are covered, namely multi-specimen and single specimen test methods. The resultingJ-R curves have also been evaluated to obtain values of the initiation toughness,J _IC, following the extrapolation and interpolation schemes prescribed by ASTM E813-81 and ASTM E813-87 test procedures, respectively. The results show that the multiple specimen unloading method and the single specimen partial unloading compliance method can be used to generate comparable crack growth resistanceJ-R curves of the toughened nylons. The value ofJ _IC for the crystalline rubber-toughened nylon was approximately twice the value obtained for the amorphous rubber-toughened nylon. The former material also exhibited a greater resistance to ductile crack growth.     

Time-of-flight secondary ion mass spectrometry as a tool for studying segregation phenomena at nickel–YSZ interfaces

Through a study of Ni–YSZ interfaces it is shown that time-of-flight-secondary ion mass spectrometry (TOF-SIMS) is a powerful and convenient tool for the analysis of ultra thin layers of segregated material at the interfaces and on free surfaces. Two different types of Ni, “pure Ni” (99.995% Ni) and “impure Ni” (99.8% Ni) were investigated. The contact areas on the YSZ and areas outside the contacts were examined with XPS and TOF-SIMS. The impure nickel causes a relatively larger amount of impurities to accumulate at the contact area, e.g. oxides of Mn, Ti, Si and Na. Some impurities migrate to the area outside the contact area. Even though on a larger scale the impurities seem to be homogeneously distributed, detailed analyses in and outside the contact area show the presence of impurity particles, and that the surface species are inhomogeneously distributed amongst the different grains. The extremely low detection limit, the small probe depth, the image capability, and the ease of elemental identification make TOF-SIMS an obvious choice as an analytical tool for studying segregation phenomena at metal–ceramic interfaces such as Ni–YSZ interfaces. XPS, being a quantitative technique, was used as a complementary technique to TOF-SIMS, which is not directly a quantitative technique.     

Synthesis and magnetic properties of novel fully conjugated polymeric complexes containing 1,10‐phenanthroline

A novel fully conjugated polymer containing 1,10‐phenanthroline (DAPcDOD) was first synthesized by the polycondensation of 2,7‐dimethyl‐2,4,6‐octatriene‐1,8‐dial with 5,6‐diamine‐1,10‐phenanthroline. Three polymeric complexes were first prepared by the reaction of DAPcDOD with NiSO₄, CoCl₂, and FeSO₄, respectively. The structures of the polymer and the complexes were characterized by IR, ¹H‐NMR, and elemental analysis. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 5 K and as a function of temperature (5–300 K) at a magnetic field strength of 30 kOe. The results show that DAPcDOD–Ni²⁺ and DAPcDOD–Co²⁺ were soft ferromagnets, whereas DAPcDOD–Fe²⁺ exhibited the features of an antiferromagnet. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008