Spectroscopic investigation of Cr(III)- and Cr(VI)-treated nanoscale zerovalent iron

The reaction of hexavalent chromium (Cr(VI)) with zerovalent iron (Fe0) during soil and groundwater remediation is an important environmental process. This study used several techniques including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy to investigate nanometer scale Fe0 particles (nano Fe0) treated with Cr(III) and Cr(VI). X-ray diffraction and XPS analyses of oxidized nano Fe0 showed the crystalline Fe(III) phase is composed of lepidocrocite (gamma-FeOOH). Results of XPS Cr 2p data and Cr K-edge X-ray absorption near edge spectroscopy (XANES) provided evidence that Cr(VI) was entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after reaction. In addition, XPS and XANES results of Cr(III) precipitated as Cr(OH)3 in the presence of corroding nano Fe0 were nearly identical to the Cr(VI)-nano Fe0 reaction product. Detailed analysis of XPS O 1s line spectra revealed that both Cr(III)- and Cr(VI)-treated nano Fe0 yielded a predominantly hydroxylated Cr(OH)3 and/ or a mixed phase CrxFe(1 - x)(OH)3 product. The structure of the Cr(III)- and Cr(VI)-treated nano Fe0 determined using extended X-ray absorption fine structure spectroscopy (EXAFS) revealed octahedral Cr(III) with Cr-O interatomic distances between 1.97 and 1.98 A for both Cr(III) and Cr(VI) treatments and a pronounced Cr-Cr second interatomic shell at 3.01 A. Our results suggest that the reaction product of Cr(VI)-treated nano Fe0 is either a poorly ordered Cr(OH)3 precipitate or possibly a mixed phase CrxFe(1 - x)(OH)3 product, both of which are highly insoluble under environmental conditions.     

Polymer assisted isolation of hydroxyapatite from Thunnus obesus bone

The combination of micro and nanostructured hydroxyapatite (HAp) was isolated from Thunnus obesus bone via thermal calcination method in the presence of polymers such as poly ethylene glycol (PEG), poly (ethylene glycol)-block-poly (propylene glycol)-block-poly (ethylene glycol) (PEG-PPG-PEG) and poly vinyl alcohol (PVA). The thermal stability, crystalline phase, chemical composition and morphology of the derived HAp were characterized by thermal gravimetric analysis, X-ray diffraction analysis, Fourier transform infrared spectroscopy and field emission scanning electron microscopy analysis. The physicochemical characteristic examination revealed that derived HAp was coherent with standard HAp data. Moreover, FE-SEM depicted significant difference in the crystal size of HAp derived with thermal calcination, with and without added polymers. The crystallinity of HAp isolated in the presence of polymer was lower than that obtained in the absence of polymers. The biocompatibility of the derived HAp crystals was checked with MC3T3-E1 osteoblastic cells by MTT assay and Hoechst-33342 staining. The biocompatibility of HAp derived by polymer assisted thermal calcination method revealed that it is less toxic as compared to HAp derived in the absence of polymer. As an inference, polymer assisted thermal calcination derived HAp is good in terms of the presence of combined micro and nanostructured HAp and its low toxicity will bring about new orthopaedic applications.     

Comparison between Wild and Hatchery Populations of Korean Pen Shell (Atrina pectinata) Using Microsatellite DNA Markers

Pen shell (Atrina pectinata) is a popular food source with a high commercial value in a number of Asian Pacific areas. The natural A. pectinata population has been declining continuously over the past several decades. Microsatellite DNA markers are a useful DNA-based tool for monitoring the genetic variation of pen shell populations. In this study, 20 polymorphic microsatellite (MS) DNA markers were identified from a partial genomic pen shell DNA library enriched in CA repeats, and used to compare allelic variation between wild and hatchery pen shell populations in Korea. A total of 438 alleles were detected at the 20 MS loci in the two populations. All loci were easily amplified and demonstrated allelic variability, with the number of alleles ranging from 5 to 35 in the wild population and from 5 to 22 in the farmed population. The average observed and expected heterozygosities were 0.69 and 0.82, respectively, in the hatchery samples and 0.69 and 0.83, respectively, in the wild samples. Statistical analysis of fixation index (F(ST)) and analysis of molecular variance (AMOVA) showed minor, but significant, genetic differences between the wild and hatchery populations (F(ST) = 0.0106, CI(95%) = 0.003-0.017). These microsatellite loci may be valuable for future aquaculture and population genetic studies for developing conservation and management plans. Further studies with additional pen shell samples are needed to conclusively determine the genetic diversity between the wild and hatchery populations.     

Effect of Nafion ionomer and catalyst in cathode layers for the direct formic acid fuel cell with complex capacitance analysis on the ionic resistance

Using platinum (Pt) black and carbon-supported Pt (Pt/C) as cathode catalysts, membrane-electrode assemblies (MEAs) were fabricated with various Nafion ionomer content, and their direct formic acid fuel cell (DFAFC) performances were investigated. In MEAs incorporating Pt black catalysts, the current density at 0.6 V was highest at ionomer/catalyst volume ratio of 1.0, which was consistent with the electrochemical active area (EAS) variation measured by cyclic voltammetry. However, the current density measured at 0.3 V, the cell performance increased with Nafion ionomer content, especially at low ionomer loading, indicating that proton transport rate played an important role. The variation in ionic resistance (R_ion) of cathode layers with Nafion ionomer content was experimentally confirmed by using the complex capacitance analysis of impedance data implemented with nitrogen (cathodes)/hydrogen (anodes) atmosphere. For Pt/C, the layer thickness and EAS of cathode were larger than those of MEA cathode using Pt black; and the current densities at 0.6 V were lower than those of Pt black, suggesting that smaller fraction of EAS was utilized.     

Effects of (NH4)2SO4 and BTA on the nanostructure of copper foam prepared by electrodeposition

Copper foam with dendritic copper nanostructure was synthesized by an electrodeposition process using hydrogen bubbles as dynamic templates. To modify the morphology of the copper nanostructure in the foam walls, (NH₄)₂SO₄ and BTA (benzotriazole) were introduced into the electrolytic bath as chemical additives, and their influences on the morphologies and the structural characteristics of copper deposits were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mechanical strength and stiffness of the copper foam were evaluated by the compression test. The corncob-like deposits of the copper foam were changed to needle-like nanodendrites by the addition of (NH₄)₂SO₄, which significantly improved the mechanical strength and stiffness due to the self-supporting effects of the tightly interlocked needle-like nanodendrites. In contrast, the copper foam prepared from the solution with (NH₄)₂SO₄ and BTA shows high ductility but low mechanical strength due to the formation to grape-like copper deposits. Both the copper foams exhibited higher mechanical properties than the one with corncob-like deposits formed in the additive-free solution. The reaction mechanism of (NH₄)₂SO₄ and BTA on the nanostructure of the copper foam at high cathodic current density was clarified by analyzing the effects of the additives on the copper deposition reaction and hydrogen gas evolution reaction, respectively.     

Effect of wall friction on variation of formwork pressure over time in self-consolidating concrete

In order to accurately predict the varying of formwork pressure over time, it is necessary to consider various factors influencing the development of formwork pressure. A prediction model has been previously proposed, but that model has some limitations in that only intrinsic material characteristics are taken into account. Extrinsic effects such as wall friction, formwork flexibility, and external temperature are excluded in the model. This study focuses on the wall friction effect as one of the extrinsic factors. First, by incorporating the intrinsic model and friction stress acting on the interface, a method of calculating formwork pressure considering the wall friction effect is suggested. To find out how much friction stress is acting on the interface and how it varies over time, formwork pressure tests were performed with circular column formworks having three different diameters. In these columns, the vertical pressure at the bottom and the lateral pressures were measured. To calibrate parameters of the intrinsic model for the same material as that used in the formwork pressure tests, additional tests were conducted with a specially designed apparatus that can exclude effects of extrinsic factors. From tests and analysis results, it was found that wall friction greatly affects the variation of formwork pressure over time. The newly suggested calculation method can give a good prediction of real formwork pressure.     

Assembly of strands of multiwall carbon nanotubes and gold nanoparticles using alkanedithiols

Multiwall carbon nanotubes and gold nanoparticles (MWCNT–AuNP) were assembled into strands by cross-linking with alkanedithiols. Long MWCNT strands were first shortened to ∼0.25 μm by chemical oxidation followed by ball-milling, and then thiolated by reaction with cysteamine. The thiol groups on the surfaces of the MWCNT strands combined with Au nanoparticles to produce MWCNT–AuNP strands. A simple mixing of these strands with alkanedithiols resulted in an assembly of strands linked by the alkanedithiols which adsorbed onto the surfaces of the AuNPs attached to the MWCNT–AuNP strands. Short MWCNT–AuNP strands connected to one another in a parallel arrangement, whereas long strands assembled in a crossing arrangement. The possibility of using this method to chemically bond MWCNTs to lower the contact resistance of thin CNT films is discussed.     

Alignment of a nematic liquid crystal on nano‐grooved material

We demonstrate the alignment characteristics of a nematic liquid crystal on the surface of a nanoimprinted material that is a functionally graduated composite suitable for the alignment of a liquid crystal on a groove surface processed by nanoimprinting lithography. With the electro‐optic characteristics shown in twisted nematic and in‐plane switching modes, the potential liquid crystal applications are examined. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of poly(ε‐caprolactone)/clay nanocomposites using polyhedral oligomeric silsesquioxane surfactants as organic modifier and initiator

Poly(ε‐caprolactone)/clay nanocomposites were synthesized by in situ ring‐opening polymerization of ε‐caprolactone in the presence of montmorillonite modified by hydroxyl functionalized, quaternized polyhedral oligomeric silsesquioxane (POSS) surfactants. The octa(3‐chloropropyl) polyhedral oligomeric silsesquioxane was prepared by hydrolytic condensation of 3‐chloropropyltrimethoxysilane, which was subsequently quaternized with 2‐dimethylaminoethanol. Montmorillonite was modified with the quaternized surfactants by cation exchange reaction. Bulk polymerization of ε‐caprolactone was conducted at 110°C using stannous octoate as an initiator/catalyst. Nanocomposites were analyzed by X‐ray diffraction, transmission electron microscopy, thermo gravimetric analysis, and differential scanning calorimetry. Hydroxyl functionalized POSS was employed as a surface modifier for clay which gives stable clay separation for its 3‐D structure and also facilitates the miscibility of polymer with clay in the nanocomposites due to the star architecture. An improvement in the thermal stability of PCL was observed even at 1 wt % of clay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011