Studies on mechanism of single-walled carbon nanotube formation

We presented detailed studies of the formation of single-walled carbon nanotubes by an aerosol method based on the introduction of pre-formed catalyst particles into conditions leading to carbon nanotube synthesis. Carbon monoxide and iron nanoparticles were used as a carbon source and a catalyst, respectively. The vital role of etching agents such as CO2 and H2O in CNT formation was demonstrated on the basis of on-line Fourier-transform infrared spectroscopy measurements. Hydrogen was shown to participate in the reaction of carbon release and to prevent the oxidation of the catalyst particles and the hot wire. The addition of H2 and small amounts of CO2 and H2O led to an increase in the carbon nanotube lengths. The catalyst particle evaporation process inside the reactor was found to become significant at temperatures higher than 1100 degrees C. The carbon nanotube growth was found to occur at a temperature of around 900 degrees C in the heating section of the reactor by in situ sampling and the growth rate was calculated to exceed 1.1 microm/s. A detailed analysis of possible processes during carbon nanotube formation revealed heptagon transformation as a limiting stage. A mechanism for carbon nanotube formation was proposed.     

Kinetics of the solvent-free hydrogenation of 2-methyl-3-butyn-2-ol over a structured Pd-based catalyst

The solvent-free selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) was studied over a Pd/ZnO structured catalyst and compared to its behavior in water-assisted conditions. The catalytic behavior was correlated with the surface properties of the catalysts which were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The catalyst showed high selectivity and stability with the performance being superior to that of the industrial Lindlar catalyst (50%). The addition of a sulphur-containing modifier in the reaction mixture was found to affect the activity and to hinder the over-hydrogenation reaction. The MBE yield of 97% was attained at MBY conversion >99%. The reuse of the catalyst showed that it deactivated by a 38% and that its selectivity slightly increased (0.5%) over 10 runs. The reaction kinetics was modeled using a Langmuir–Hinshelwood mechanism considering competitive adsorption for the organic species and dissociative adsorption for hydrogen. The kinetic experiments were planned and the results analyzed following a design of experiments (DOE) methodology. This approach led not only to a robust model that predicts the reaction rate in a wide range of reaction conditions but also to the determination of its kinetic parameters.     

营造“创智天地”

文章分析了上海创智天地项目的选址原因及营造挑战,重点介绍了创智天地应对的社区理念及策略。     

Development of a model for assessing methane formation in rising main sewers

Significant methane formation in sewers has been reported recently, which may contribute significantly to the overall greenhouse gas emission from wastewater systems. The understanding of the biological conversions occurring in sewers, particularly the competition between methanogenic and sulfate-reducing populations for electron donors, is an essential step for minimising methane emissions from sewers. This work proposes an extension to the current state-of-the-art models characterising biological and physicochemical processes in sewers. This extended model includes the competitive interactions of sulfate-reducing bacteria and methanogenic archaea in sewers for various substrates available. The most relevant parameters of the model were calibrated with lab-scale experimental data. The calibrated model described field data reasonably well. The model was then used to investigate the effect of several key sewer design and operational parameters on methane formation. The simulation results showed that methane production was highly correlated with the hydraulic residence time (HRT) and pipe area to volume (A/V) ratio showing higher methane concentrations at a long HRT or a larger A/V ratio.     

A Hybrid Geometric–Statistical Deformable Model for Automated 3-D Segmentation in Brain MRI

We present a novel 3-D deformable model-based approach for accurate, robust, and automated tissue segmentation of brain MRI data of single as well as multiple magnetic resonance sequences. The main contribution of this study is that we employ an edge-based geodesic active contour for the segmentation task by integrating both image edge geometry and voxel statistical homogeneity into a novel hybrid geometric-statistical feature to regularize contour convergence and extract complex anatomical structures. We validate the accuracy of the segmentation results on simulated brain MRI scans of both single T1-weighted and multiple T1/T2/PD-weighted sequences. We also demonstrate the robustness of the proposed method when applied to clinical brain MRI scans. When compared to a current state-of-the-art region-based level-set segmentation formulation, our white matter and gray matter segmentation resulted in significantly higher accuracy levels with a mean improvement in Dice similarity indexes of 8.55% (p<0.0001) and 10.18% (p<0.0001), respectively.     

The suppression of tin whisker growth by the coating of tin oxide nano particles and surface treatment

Tin oxide nano particles dispersed in water solution were sprayed on the tin-plated copper surface and served as coating layer in order to study its effect on the prevention of tin whisker formation. The results indicated that tin oxide nano particles could inhibit the growth of tin whiskers to certain extent. Many hillocks instead of long whiskers grew on the surfaces of samples that underwent 25, 40 and 60 °C annealing for 10 weeks. Furthermore, a strong etchant and polishing were applied to the tin-plated samples. XPS results showed that the surface oxide was removed by surface treatments; the surfaces were then coated by spraying nano particles. It is found that the coherency of the re-grown oxide during annealing was reduced, leading to the growth of hillocks instead of long whiskers. This approach seems to successfully enhance the relaxation of stress to prevent the growth of long whiskers.     

The Effects of Solid-State Aging on the Intermetallic Compounds of Sn-Ag-Bi-In Solders on Cu Substrates

The growth behavior of the intermetallic compounds that formed at the interfaces between Sn-Ag-Bi-In solders and Cu substrates during solid-state aging is investigated. The compositions of the intermetallic compounds are Cu₃(Sn,In) near the Cu substrates and Cu₆(Sn,In)₅ near the solders; very little Bi or Ag was dissolved in the compounds. The aging temperatures were 120°C, 150°C, and 180°C for 5 days, 10 days, 20 days, and 40 days. The change in the morphology of Cu₆(Sn,In)₅ from scallop type to layer type was prominent at the aging temperature of 180°C. The thickness of the compound layers did not vary much at the lower aging temperatures but followed the diffusion- controlled mechanism at 180°C. Massive Kirkendall voids were observed in Cu₃(Sn,In) layers at the aging temperature of 180°C.     

Optical properties of solution-processable semiconducting TiOx thin films for solar cell and other applications

The optical properties of solution-processable semiconducting titanium suboxide (TiOx) thin films were investigated as a function of wavelength (350-800 nm) using ellipsometric and optical reflection technique. The variation of refractive index under different thermal annealing conditions (room temperature to 900 °C) was studied. The increase in refractive index with high-temperature thermal annealing process was observed, allowing the opportunity to obtain refractive index values from 1.77 to 2.57 at a wavelength of 600 nm. The x-ray diffraction and atomic force microscopy studies indicate that the index variation is due to the TiOx phase, density, and morphology changes under thermal annealing. The TiOx thin films have applications in organic and inorganic solar cells as well as other optical and photonic devices. We show that TiOx thin films can be used as an effective antireflection layer for Si solar cells.     

Ultra acidic strong cation exchange enabling the efficient enrichment of basic phosphopeptides

We present a straightforward method to enrich phosphopeptides with multiple basic residues, an under-represented class in common enrichment strategies. Our method is based on a two-dimensional strong cation exchange (SCX) strategy, operating at two different acidic pHs, enabling both separation and enrichment of different classes of phosphopeptides. The principle of enrichment is based on the change of net charge of phosphorylated peptides under strong acidic conditions in the second SCX, whereas the net charge of regular peptides remains unchanged, thus enabling separation based on net charge. Application of our tandem SCX approach to a modest amount of human cells allowed the identification of over 10,000 unique "basic" phosphopeptides of which many represent putative targets of basophilic kinases.     

Durability of different carbon nanomaterial supports with PtRu catalyst in a direct methanol fuel cell

PtRu catalysts with similar particle size and composition were deposited on three different carbon supports: Vulcan, graphitized carbon nanofibers (GNF) and few-walled carbon nanotubes (FWCNT) and their performance for methanol oxidation was studied in an electrochemical cell and in a single cell DMFC. The electrochemical results indicate that with PtRu/GNF and PtRu/FWCNT higher current densities are obtained and oxidation intermediates deactivate the surface less compared to the same catalyst on Vulcan support. Conversely, PtRu/Vulcan provided the highest open circuit voltage OCV and current densities in DMFC experiments due to a well-optimized electrode layer structure. Because stability is a key requirement for fuel cell commercialization, 6-day-long fuel cell stability tests were carried out, showing that PtRu/Vulcan degraded significantly. This was due to the collapse of the secondary structure of the electrode layer revealed by post characterization of the membrane electrode assembly (MEA) with SEM and TEM. PtRu/GNF exhibited slightly poorer initial performance but better stability because the structure of the anode layer was maintained. PtRu/FWCNT showed the worst initial performance and long-term stability. The good stability of non-optimized PtRu/GNF MEAs shows the potential of these novel nanocarbon supported catalysts as stable fuel cell components after proper MEA optimization.