Mechanisms of electro-assisted persulfate/nano-Fe0 oxidation process: Roles of redox mediation by dissolved Fe.

Mechanisms involved in an electrochemically assisted oxidation process using persulfate and nanosized zero-valent iron (NZVI) were elucidated. Initially, Fe0 acted as a source of Fe2+ to activate the persulfate, then Fe2+/Fe3+ redox mediation between cathode and persulfate played a decisive role in persulfate activation at a current density low enough not to inhibit Fe0 corrosion. An excessive current density which resulted in a low cathodic potential limited Fe0 corrosion and therefore limited the supply of dissolved Fe to activate the persulfate. Direct oxidation of phenol at the anode therefore became more important under the excessive current density than oxidation by sulfate radicals. At a low current density, Fe0 in the NZVI particles was completely transformed into iron (oxyhydr)oxides such as ferrihydrite, lepidocrocite, and magnetite. Fe0 was transformed into Fe2+ little when the current density was high. Increasing the current density increased the energy cost by increasing the amount of electrical energy dissipated in side reactions that decreased sulfate radical formation. The results indicated that a low current density can generally be used to give a high reaction rate and a high energy efficiency and that a high current density can be used when the NZVI particles need to be preserved.

Carbonation/granulation of mine tailings using a MgO/ground-granule blast-furnace-slag binder.

A carbonation/granulation process for treating mine tailings using a MgO/ground-granule blast-furnace-slag (GGBS) binder was developed. The materials were mixed and granules produced using a granulator, then the granules were cured in a CO2 atmosphere. The optimum granulator rotation speed and retention time were 60 rpm and 7 min, respectively. The binder composition MgO0.5GGBS0.5 and binder: mine tailings ratio 3:10 gave the strongest granules. Carbonation generally increased the granule strength, but different CO2 concentrations, between 0.04% and 100%, changed the granule strength to different degrees. Granules cured in 20% CO2 for 28 d had a strength of 4.71 MPa, which was higher than the strengths of granules cured in other CO2 concentrations and of granules produced using Portland cement. The granules had relatively high CO2 storage capacities of 0.157-0.167 kg CO2/kg binder and good acid-neutralizing capacities (higher than the acid-neutralizing capacity of granules produced using Portland cement). The strength of the granules cured in 20% CO2 for 28 d was probably mainly attributed to the formation of hydromagnesite during carbonation. The hydromagnesite contributed dense and connected structures within the granules. The granules produced show great potential for use as aggregates for reclamation work and backfilling in mining areas.

Effect of CO2 concentration on strength development and carbonation of a MgO-based binder for treating fine sediment.

We previously described a MgO-based binder for treating fine sediment and simultaneously store CO2. Here, we describe a study of the physical/mechanical characteristics and carbonation reactions of the MgO-based binder used to solidify/stabilize fine sediment in atmospheres containing different CO2 concentrations. Carbonation of the sediment treated with the MgO-based binder at the atmospheric CO2 concentration markedly improved the compressive strength of the product. The compressive strength was 4.78 MPa after 365 days of curing, 1.3 times higher than the compressive strength of sediment treated with portland cement. This improvement was caused by the formation of carbonation products, such as hydromagnesite, nesquehonite, and lansfordite, and the constant high pH (~ 12) of the specimen, which favored the growth of hydration products such as calcium silicate hydrates and portlandite. Very low compressive strengths were found when 50 and 100% CO2 atmospheres were used because of excessive formation of carbonation products, which occupied 78% of the specimen depth. Abundant carbonation products increased the specimen volume and decreased the pH to 10.2, slowing the growth of hydration products. The absence of brucite in specimens produced in a 100% CO2 atmosphere indicated that MgO carbonation is favored over hydration at high CO2 concentrations.

Activation of Persulfate by Nanosized Zero-Valent Iron (NZVI): Mechanisms and Transformation Products of NZVI.

The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe0(s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe2+. The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe2+. In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.

Effect of Liquid Media on the Formation of Multi-Layer Graphene-Synthesized Metal Particles.

We report a simple approach for the production of copper nanoparticles by a wire explosion process that creates different structures in deionized (DI) water versus isopropyl alcohol (IPA) liquid media. In DI water, copper nanoparticles (CNs) are formed, while multi-layer graphene-synthesized copper nanoparticles (MGCNs) with a high degree of graphitization are formed in the IPA liquid media. The nanoparticles have an average diameter ranging from 10 nm to 300 nm and a quasi-spherical morphology. The morphologies and sizes of nanoparticles formed via this method were characterized by high-resolution transmission electron microscopy (HRTEM), field-emission scattering electron microscopy (FESEM), and analysis of dynamic light scattering (DLS). The microstructures and chemical bonding of the nanoparticles were studied by X-ray diffraction (XRD), Raman spectra measurement, and X-ray photoelectron spectroscopy (XPS). This results show an easily reproducible way to synthesize metal-core nanoparticles with multi-layer graphene shells based onto the liquid media used during synthesis. These materials can be used in the field of energy storage and as additives in the near future.

Power Enhancement of Lithium-Ion Batteries by a Graphene Interfacial Layer.

We achieved a method for power enhancement of heavy-duty lithium-ion batteries (LIBs) by synthesizing a graphene interfacial layer onto the anode copper current collector (ACCC). We tested fabricated coin cells, which used either 35-µm-thick rolled pristine copper foil or graphene synthesized onto the pristine copper foil for power output estimation of the LIBs. We observed the copper surface morphology with a scanning electron microscope (SEM). Raman spectroscopy was used to measure the bonding characteristics and estimate the layers of graphene films. In addition, transmittance and electrical resistance were measured by ultra-violet visible near-infrared spectroscopy (UV-Vis IR) and 4 point probe surface resistance measurement. The graphene films on polyethylene terephthalate (PET) substrate obtained a transmittance of 97.5% and sheet resistance of 429 Ω/square. Power enhancement performances was evaluated using LIB coin cells. After 5C current discharge rate of -1.7 A/g reversible capacity of 293 mAh/g and 326 mAh/g were obtained for pristine and synthesized graphene anode current collectors, respectively. The graphene synthesized onto the ACCC showed superior power performance. The results presented herein demonstrate a power enhancement of LIBs by a decrease in electron flow resistivity between active materials and the ACCC and removal of the native oxide layer on the anode copper surface using high quality graphene synthesized onto the ACCC.

Electroless nickel alloy deposition on SiO2 for application as a diffusion barrier and seed layer in 3D copper interconnect technology.

Electroless Ni-P films were investigated with the aim of application as barrier and seed layers in 3D interconnect technology. Different shapes of blind-via holes were fabricated with a deep reactive ion etcher and SiO2 formed on these holes as an insulating layer. The surface of the substrate has been made hydrophilic by O2 plasma treatment with 100 W of power for 20 min. Electroless Ni-P films were deposited as both a diffusion barrier and a seed layer for Cu filling process. Prior to plating, substrates were activated in a palladium chloride solution after sensitization in a tin chloride solution with various conditions in order to deposit uniform films in TSV. After the formation of the electroless barrier layer, electro Cu was plated directly on the barrier layer. Ni-P films fabricated in blind-via holes were observed by scanning electron microscope. Energy dispersive spectroscopy line scanning was carried out for evaluating the diffusion barrier properties of the Ni-P films. The electroless Ni-P layer worked well as a Cu diffusion barrier until 300 degrees C. However, Cu ions diffused into barrier layer when the annealing temperature increases over 400 degrees C.

Nonsurgical treatment of an incompletely excised primary adenocarcinoma of nonpigmented ciliary epithelium.

Primary adenocarcinoma of the nonpigmented ciliary epithelium (NPCE) is a very rare disease and the majority of acquired cases were treated by enucleation. We report the case of a 19-year-old man who had an adenocarcinoma arising from the NPCE. The tumor was found incidentally due to changed pupil shape. An excisional biopsy was performed and histopathological examination showed primary adenocarcinoma of the NPCE with a positive resection margin. Because of the positive resection margin and to save the eye, radiotherapy rather than enucleation was performed, followed by chemotherapy. Two years after the diagnosis, the patient continues to be followed up without evidence of relapse or cataract change. Our case suggests that adjunctive radiotherapy should be considered as a sight-saving treatment modality for primary malignant tumors of the NPCE.