Failure of pyrolysis coils coated with anit-coking film in an ethylene cracking plant

This paper presents a specific kind of failure in ethylene cracking coils coated with anticoking film. It investigates a case in which the coils made of 35Cr 45Ni high temperature alloy failed within two years of operation. The damage occurred due to heavy oxidation in localized regions of the coil resulting in the formation of blisters, which eventually failed by cracking. The mechanism involved was determined by studying the oxidized samples under a scanning electron microscope with an energy dispersive system and is attributed to the presence of rare earth metals in the anti-coking film and inherent casting defects in the base alloy. The cerium present in the anti-coking film diffused preferentially to a defect site in the parent alloy thereby resulting in its segregation which further led to embrittlement. (C) 2014 Elsevier Ltd. All rights reserved.

Fourier spectrum based extraction of an equivalent trap state density in indium gallium zinc oxide transistors

Segregating the dynamics of gate bias induced threshold voltage shift, and in particular, charge trapping in thin film transistors (TFTs) based on time constants provides insight into the different mechanisms underlying TFTs instability. In this Letter we develop a representation of the time constants and model the magnitude of charge trapped in the form of an equivalent density of created trap states. This representation is extracted from the Fourier spectrum of the dynamics of charge trapping. Using amorphous In-Ga-Zn-O TFTs as an example, the charge trapping was modeled within an energy range of Delta E-t approximate to 0.3 eV and with a density of state distribution as D-t(Et-j) = D-t0 exp(-Delta E-t/kT) with D-t0 = 5.02 x 10(11) cm(-2) eV(-1). Such a model is useful for developing simulation tools for circuit design. (C) 2014 AIP Publishing LLC.

Impact of spray flux density and vacuum annealing on the transparent conducting properties of doubly doped (Sn plus F) zinc oxide films deposited using a simplified spray technique

In this investigation transparent conducting properties of as-deposited and annealed ZnO:Sn:F films deposited using different spray flux density by changing the solvent volume (10 mL, 20 mL ... 50 mL) of the starting solutions have been studied and reported. The structural analyses of the films indicate that all the films have hexagonal wurtzite structure of ZnO with preferential orientation along (002) plane irrespective of the solvent volume and annealing treatment whereas, the overall crystalline quality of the films is found to be enhanced with the increase in solvent volume as well as with annealing. This observed enhancement is strongly supported by the optical and surface morphological results. From the measurements of electrical parameters, it is seen that, the annealed films exhibit better electrical properties compared to the as-deposited ones. Annealing has caused agglomeration of grains as confirmed by the surface morphological studies. Also, the annealing process has led to an improvement in the optical transparency as well as band gap. It is found from the analyses of the characteristics of the as- deposited and annealed films that the annealed film deposited from starting solution having solvent volume of 50 mL is optimal in all respects, as it possesses all the desirable characteristics including the quality factor (1.60 x 10(-4) (Omega/sq.)(-1)). (C) 2014 Elsevier Ltd. All rights reserved.

Effect of film thickness and annealing on optical properties of TiO2 thin films and electrical characterization of MOS capacitors

Titanium dioxide (TiO2) thin films were deposited on glass and silicon (100) substrates by the sol-gel method. The influence of film thickness and annealing temperature on optical transmittance/reflectance of TiO2 films was studied. TiO2 films were used to fabricate metal-oxide-semiconductor capacitors. The capacitance-voltage (C-V), dissipation-voltage (D-V) and current-voltage (I-V) characteristics were studied at different annealing temperatures and the dielectric constant, current density and resistivity were estimated. The loss tangent (dissipation) increased with increase of annealing temperature.

Glass, Gel, and Liquid Crystals: Arrested States of Graphene Oxide Aqueous Dispersions

Colloidal systems with competing interactions are known to exhibit a range of dynamically arrested states because of the systems' inability to reach its underlying equilibrium state due to intrinsic frustration. Graphene oxide (GO) aqueous dispersions constitute a class of 2D-anisotropic colloids with competing interactions long-range electrostatic repulsion, originating from ionized groups located on the rim of the sheets, and weak dispersive attractive interactions originating from the unoxidized graphitic domains. We show here that aqueous dispersions of GO exhibit a range of arrested states, encompassing fluid, glass, and gels that coexist with liquid-crystalline order with increasing volume fraction. These states can be accessed by varying the relative magnitudes of the repulsive and attractive forces. This can be realized by changing the ionic strength of the medium. We observe at low salt concentrations, where long-range electrostatic repulsion dominates, the formation of a repulsive Wigner glass, while at high salt concentrations, when attractive forces dominate, the formation of gels exhibits a nematic to columnar liquid-crystalline transition. The present work highlights how the chemical structure of GO hydrophilic ionizable groups and hydrophobic graphitic domains coexisting on a single sheet gives rise to a rich and complex array of arrested states.

Exploiting oriented attachment in stabilizing La3+-doped gallium oxide nano-spindles

Retaining the morphology of gallium oxide nanostructures during structural transformations or after doping with lanthanide ions is not facile. Here we report on the sonochemical synthesis of nearly monodisperse similar to 550 nm long nano-spindles of undoped and La-doped alpha-GaOOH. The transformation of as-prepared undoped and La-doped alpha-GaOOH powders into the corresponding undoped and La-doped Ga2O3 phases (alpha and beta) was achieved by carrying out controlled annealing at elevated temperatures under optimized conditions. The formation of gallium oxide nano-spindles is explained by invoking the phenomenon of oriented attachment, as amply supported by electron microscopy. Interestingly, the morphology of the gallium oxide nano-spindles remained conserved even after doping them with more than 1.4 at% of La3+ ions. Such robust structural stability could be attributed to the oriented attachment-type growth observed in the nano-spindles. The as-prepared samples and the corresponding annealed ones were thoroughly characterized by powder X-ray diffraction (PXRD), electron microscopy (SEM, TEM, and STEM-EDS) and X-ray photoelectron spectroscopy (XPS). Finally, photoluminescence from the single-crystalline undoped and La-doped beta-Ga2O3 was explored.

High quality oxide-free metallic nanoparticles: a strategy for synthesis through laser ablation in aqueous medium

The paper explores the synthesis of oxide-free nanoparticles of Ag and Cu through laser ablation of pure targets under aqueous medium and tuning the quality and size through addition of Polyvinylpyrrolidone (PVP) in the medium. The size distribution of nanoparticles reduces from 37 +/- 30 nm and 13 +/- 5 nm to 32 +/- 12 nm and 4 +/- 1 nm for Ag and Cu with changes in PVP concentration from 0.00 to 0.02 M, respectively. Irregular shaped particles of Ag with Ag2O phase and a Cu-Cu2O core-shell particles form without the addition of PVP, while oxide layer is absent with 0.02 M of PVP. The recent understanding of the mechanism of particle formation during laser ablation under liquid medium allows us to rationalize our observation.

Tin-Incorporation Induced Changes in the Microstructural, Optical, and Electrical Behavior of Tungsten Oxide Nanocrystalline Thin Films Grown Via Spray Pyrolysis

Undoped and Sn-doped WO3 thin films were grown on cleaned glass substrates by chemical spray pyrolysis, using ammonium tungstate (NH4)(2)WO4 as the host precursor and tin chloride (SnCl4 center dot 5H(2)O) as the source of dopant. The XRD spectra confirm the monoclinic structure with a sharp narrow peak along (200) direction along with other peaks of low relative intensities for all the samples. On Sn doping, the films exhibit reduced crystallinity relative to the undoped film. The standard deviation for relative peak intensity with dopant concentration shows enhancement in heterogeneous nucleation growth. As evident from SEM images, on Sn doping, appearance of island-like structure (i.e., cluster of primary crystallites at few places) takes place. The transmittance has been found to decrease in all the Sn-doped films. The optical band gap has been calculated for both direct and indirect transitions. On Sn doping, the direct band gap shows a red shift and becomes 2.89 eV at 2 at.% doping. Two distinct peaks, one blue emission at 408 nm and other green emission at 533 nm, have been found in the PL spectra. Electrical conductivity has been found to increase with Sn doping.

Formation of hierarchical structures of Fe2O3 by the liquid-liquid interface technique

We report the formation of dendritic hierarchical structures of alpha-Fe2O3 and nanostructures of Fe2O3 by the simple liquid-liquid interface method. The morphology of thin films determined by high-resolution scanning electron microscopy shows nanorods, nanosheets and dendritic Fe2O3. The identification of phases of iron oxide structures is carried out by using XRD and XPS studies. XRD and XPS measurements point out the highly crystalline dendritic alpha-Fe2O3 phase and the mixed phase of alpha- and gamma-Fe2O3 nanostructures. The magnetic measurement also suggests the presence of a mixed phase in the sample grown for 72 hours.

Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide: outstanding mechanical properties

A unique strategy was adopted here to improve the compatibility between the components of an immiscible polymer blend and strengthen the interface. PMMA, a mutually miscible polymer to both PVDF and ABS, improved the compatibility between the phases by localizing at the blends interface. This was supported by the core-shell formation with PMMA as the shell and ABS as the core as observed from the SEM micrographs. This phenomenon was strongly contingent on the concentration of PMMA in the blends. This strategy was further extended to localize graphene oxide (GO) sheets at the blends interface by chemically coupling it to PMMA (PMMA-g-GO). A dramatic increment of ca. 84% in the Young's modulus and ca. 124% in the yield strength was observed in the presence of PMMA-g-GO with respect to the neat blends. A simultaneous increment in both the strength and the modulus was observed in the presence of PMMA-g-GO whereas, only addition of GO resulted in a moderate improvement in the yield strength. This study reveals that a mutually miscible polymer can render compatibility between the immiscible pair and can improve the stress transfer at the interface.

Zinc oxide based photocatalysis: tailoring surface-bulk structure and related interfacial charge carrier dynamics for better environmental applications

As an alternative to the gold standard TiO2 photocatalyst, the use of zinc oxide (ZnO) as a robust candidate for wastewater treatment is widespread due to its similarity in charge carrier dynamics upon bandgap excitation and the generation of reactive oxygen species in aqueous suspensions with TiO2. However, the large bandgap of ZnO, the massive charge carrier recombination, and the photoinduced corrosion-dissolution at extreme pH conditions, together with the formation of inert Zn(OH)(2) during photocatalytic reactions act as barriers for its extensive applicability. To this end, research has been intensified to improve the performance of ZnO by tailoring its surface-bulk structure and by altering its photogenerated charge transfer pathways with an intention to inhibit the surface-bulk charge carrier recombination. For the first time, the several strategies, such as tailoring the intrinsic defects, surface modification with organic compounds, doping with foreign ions, noble metal deposition, heterostructuring with other semiconductors and modification with carbon nanostructures, which have been successfully employed to improve the photoactivity and stability of ZnO are critically reviewed. Such modifications enhance the charge separation and facilitate the generation of reactive oxygenated free radicals, and also the interaction with the pollutant molecules. The synthetic route to obtain hierarchical nanostructured morphologies and study their impact on the photocatalytic performance is explained by considering the morphological influence and the defect-rich chemistry of ZnO. Finally, the crystal facet engineering of polar and non-polar facets and their relevance in photocatalysis is outlined. It is with this intention that the present review directs the further design, tailoring and tuning of the physico-chemical and optoelectronic properties of ZnO for better applications, ranging from photocatalysis to photovoltaics.

Temperature dependent current-voltage characteristics of zinc oxide nanowire/polypyrrole nanocomposite

Temperature dependent current-voltage (I-V) measurements of electrochemically prepared zinc oxide nanowire/polypyrrole (ZnONW/PPy) nanocomposite yielded non-linear I-V characteristics at temperatures between 300 and 4.5 K. The low-field conductance (G) of the ZnONW/PPy film exhibits pronounced temperature dependence with room temperature conductance (G(300K)) similar to 10(-3) S and a conductance ratio (G(300)K/G(4.5K)) of similar to 10(4), indicating dominance of significant temperature dependent charge transport processes. The conduction mechanism of the film is satisfactorily understood by extended fluctuation induced tunneling (FIT) model as the non-linear I-V characteristics fit fairly well to the extended FIT model. Further, the temperature dependence of G(o) obtained from fitting followed Sheng's model also. (C) 2014 AIP Publishing LLC.

Chemical Functionalization of Graphene To Augment Stem Cell Osteogenesis and Inhibit Biofilm Formation on Polymer Composites for Orthopedic Applications

Toward designing the next generation of resorbable biomaterials for orthopedic applications, we studied poly(epsilon-caprolactone) (PCL) composites containing graphene. The role, if any, of the functionalization of graphene on mechanical properties, stem cell response, and biofilm formation was systematically evaluated. PCL composites of graphene oxide (GO), reduced GO (RGO), and amine-functionalized GO (AGO) were prepared at different filler contents (1%, 3%, and 5%). Although the addition of the nanoparticles to PCL markedly increased the storage modulus, this increase was largest for GO followed by AGO and RGO. In vitro cell studies revealed that the AGO and GO particles significantly increased human mesenchymal stem cell proliferation. AGO was most effective in augmenting stem cell osteogenesis leading to mineralization. Bacterial studies revealed that interaction with functionalized GO induced bacterial cell death because of membrane damage, which was further accentuated by amine groups in AGO. As a result, AGO composites were best at inhibiting biofilm formation. The synergistic effect of oxygen containing functional groups and amine groups on AGO imparts the optimal combination of improved modulus, favorable stem cell response, and biofilm inhibition in AGO-reinforced composites desired for orthopedic applications. This work elucidates the importance of chemical functionalization of graphene in polymer composites for biomedical applications.

Effect of oxygen vacancies on the elastic properties of zinc oxide: A first-principles investigation

The effect of oxygen vacancies on the elastic properties of zinc oxide (ZnO) is examined using first-principles calculations based on density functional theory. Formation energies of vacancies in different types of oxygen deficient structures were analyzed to ascertain their stability. This analysis reveals that the doubly-charged oxygen vacancy under zinc-rich growth conditions is the most stable. Results show considerable degradation of some of the elastic moduli due to the presence of oxygen vacancies, which is in agreement with recent experiments. The decrease observed in elastic constants is more pronounced with increase in vacancy concentration. Further, the charge state of the defect structure was found to influence the shear elastic constants. Evaluation of elastic anisotropy of stoichiometric and oxygen deficient ZnO indicates the significant anisotropy in elastic properties and stiff c-axis orientation. (C) 2014 Elsevier B.V. All rights reserved.

Multifunctional magnetic reduced graphene oxide dendrites: Synthesis, characterization and their applications

In this paper, for the first time, we have reported the novel synthesis of reduced graphene oxide (r-GO) dendrite kind of nanomaterial. The proposed r-GO dendrite possesses multifunctional properties in various fields of sensing and separation. The dendrite was synthesized by chemical reaction in different steps. Initially, the r-GO sheet was conjugated with silane group modified magnetic nanoparticle, resulting in nanoparticle decorated r-GO. The above r-GO sheet was further reacted with a new r-GO sheet, resulting in the formation of r-GO dendrite type of structure. Multifunctional behavior of this r-GO dendrite structure was studied by different methods. First, magnetic properties were studied by vibrating sample magnetometer (VSM) and it was found that dendrite structure shows good magnetic susceptibility (180.2 emu/g). The proposed r-GO dendrite also shows a very good antibacterial behavior for Escherichia coli and excellent electrochemical behavior towards ferrocyanide probe molecule. Along with these, it also acts as a substrate for the synthesis of molecularly imprinted polymer for europium metal ion, a lanthanide. The proposed imprinted sensor shows a very high selectivity and sensitivity for europium metal ion (limit of detection= 0.019 mu g L-1) in aqueous as well as real samples. (C) 2015 Elsevier B.V. All rights reserved.