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We developed a new highly porous polyimide (PI) -silica composite with high flexibility, mechanical strength, and heat resistance. The composite was prepared by a new process consisting of (1) phase separation of a mixture of PI precursor (polyamic acid), solvent, and silicon alkoxide, induced by high-pressure CO2 (40 °C, 20 MPa), (2) silicate formation by sol-gel reaction, and (3) supercritical CO2 extraction of the solvent. The composite had a bimodal porous structure with micropores of 10-30 μm and nanopores of ∼50 nm. In the PI matrix, silica nanoparticles (< 100 nm in diameter) were highly dispersed. Porosity of the composite was 78%, which is higher than that of conventional porous PI prepared by physical foaming technique. Relative dielectric constant of the material was lower than 1.4 at 1 MHz. The porous PI-silica composite sheet was flexible enough to be folded without cracking. Notably, the Young’s modulus (0.80 GPa) and the onset decomposition temperature (600 °C) of the PI-silica composite were higher than those of conventional porous PI with similar porosity, respectively. The porous PI-silica composite is promising as a flexible thermal insulator for high-temperature use and as a thermal resistant low-k material.
In the Great Temple at Tenochtitlan, the archaeologists found more than 150 offerings with thousands of pieces, most of them made on foreign raw materials to the Basin of Mexico. Among these votive contexts, the Chamber III of stage IVa (AD 1440-1469), buried during the government of Moctezuma I, is one of the most richness offerings of the temple. Inside this context, the quantity of greenstone beads is huge, and among them, there is a group of translucent appearance that resembles the green calcite objects from the Huastec region. The purpose of this research is to confirm or discard this probable cultural origin and technological manufacture of these beads. To do that, we perform different analysis with neither non-destructive nor invasive techniques like X-Ray Fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), Raman, Optic Microscopy (OM), and Scanning Electron Microscopy (SEM). By this way we could confirm the similarities among Huastec pieces and these beads, both at mineralogical and technological levels. Based on that, and supported with some written sources from the Colonial period, we propose that these pieces could be war prizes and looted objects by pillage during the Aztec campaigns against Huastec sites; furthermore some of these goods were deposited as victory´s gifts to the gods at the Great Temple of Tenochtitlan.
Arsenic is one of the most toxic elements that can be found. Arsenic is mainly emitted by the copper, lead and zinc production, in agriculture as pesticides and herbicides. Two forms of arsenic are common in natural waters: arsenite (AsO33−) and arseniate (AsO43−), referred to as As(III) and As(V). The nano-Mg/Al-hydrotalcites present ionic exchange and adsorbent capacities. In this work, the physic-chemical characterization of nano-Mg/Al-hydrotalcites and his arsenic removal capacityis described. The solids were synthesized by the sol-gel method with Mg/Al=2 and 3 ratio. The solids and their thermal treated products were characterized by XRD, FTIR, DTA, TGA and N2 adsorption. The solids were used as adsorbents As(III) in aqueous solutions. Adsorption isotherm studies of As(III) from aqueous solution are described. The adsorbent capacity was determined using the Langmuir, Freundlich and Dubinin–Radushkevich adsorption isotherm models. The As(III) adsorption isotherm data fit best to the isotherm Freundlich model. The maximum As(III) uptake capacity by nano-Mg/Al-hydrotalcites and the heated solids were determined using the Freundlich equation and were found to 547.46, 660.15, 799.88 and 739.12 mg As(III)/g HT-Mg/Al=2, HT-Mg/Al=3, HT-Mg/Al=2 at 350°C and HT-Mg/Al=3 at 350°C respectively. In the kinetic studies using 40 mg/L concentration of As(III) solutions was obtained an excellent removal capacity in contact times less at one minute.
The effects resulting from the introduction of a controlled perturbation in a single pattern membrane on its absorption are first studied and then analyzed on the basis of band folding considerations. The interest of this approach for photovoltaic applications is finally demonstrated by overcoming the integrated absorption of an optimized single pattern membrane through the introduction of a proper pseudo disordered perturbation.
A computational algorithm has been developed to simulate the transport properties of oriented and un-oriented thin film nanocomposites of isotactic Polypropylene (iPP) and carbon nanotubes (CNT) with increasing CNT concentration. Our goal is to be able to design materials with optimal properties using these simulations. We use a cellular automata approach in a Matlab 3-D array environment. The percolation threshold is reproduced in the simulations, matching experimental data. Upon percolation, the thermal transport in the films increases sharply, due to the large difference in the thermal conductivities of the CNTs and the polymer. To verify the simulation, the thin-film samples were sheared in the melt at 200C at 1 Hz in a Linkan microscope shearing hot stage. The thermal conductivity measurements were performed on the same cell arrangement with the transport perpendicular to the thin-film plane using a DC method. The thermal conductivity is higher for the un-sheared as compared to the sheared samples. Our cellular automata simulations provide information about the microstructuremacroscopic property relation in the thin film nanocomposites and can be extended to simulations of other important materials.
Elastmeric materials are of great importance in both academic and industrial field due to the soft and highly stretchable properties. Thus, many theories and models are proposed to correlate the physical properties and structural parameters. However, in general, it is difficult to validate these models experimentally. Thus, to this day, we do not know the requirement conditions for each model or even the validity of each model. The validation of these models has been inhibited by the inherent heterogeneity of polymer networks.
Recently, we, for the first time, succeeded in fabricating polymer network with extremely suppressed heterogeneity with a novel molecular design of prepolymers. The homogeneous polymer network, called Tetra-PEG gel, is prepared by AB-type crosslink-coupling of mutually reactive tetra-arm prepolymers. In this study, we examined the models of elastic modulus and fracture energy using Tetra-PEG gel as a model system. We controlled the structural parameters with tuning the molecular weight and concentration of prepolymers, and reaction conversion of the reaction. This series of controlled network structures, for the first time, enabled us to quantitatively examine these models. We performed the stretching and tearing measurements for these polymer gels. As for the elastic modulus, we observed the shift of the models from the phantom to affine network models around the overlapping concentration of prepolymers. As for the fracture energy, we confirmed the validity of the Lake-Thomas model, which is the most popular model predicting fracture energies of elastomers.
Thin films of AgSbS2 (150 nm) are prepared (75 min at 40 °C) via chemical deposition using a solution mixture containing SbCl3, Na2S2O3 and AgNO3. As-deposited films are amorphous. When they are heated in nitrogen at 180-320 °C, crystalline cubic-AgSbS2 films are formed. They show an optical band gap 1.89 eV and photoconductivity 1.8x10-5 Ω-1cm-1. Silver antimony sulfide-selenide film, AgSb(SxSe1-x)2, is produced from the initial amorphous film when it is heated in presence of Se-vapor. XRD analysis confirms the formation of solid solution AgSbS1.25Se0.75 or AgSbSe2 depending on the extent of Se-vapor available during heating. SnO2:F/CdS/AgSbS2/C solar cell shows Voc 610 mV, Jsc 0.88 mA/cm2,FF 0.53 and η 0.28%. In SnO2:F/CdS/Sb2S3/AgSb(SxSe1-x)2/C solar cell, Voc is 582 mV, Jsc 0.99 mA/cm2, FF 0.51 and η 0.29%.
We investigated the migration behavior of rodlike double-stranded DNA (dsDNA) in polymer gels and polymer solutions. Tetra-PEG gel, which has a homogeneous network structure, was utilized as a model system, allowing us to systematically tune the polymer volume fraction and molecular weight of network strand. Although we examined the applicability of the existing models, all the models failed to predict the migration behavior. Thus, we proposed a new model based on the Ogston model, which well explained the experimental data of polymer solutions and gels. The polymer volume fraction determined the maximum mobility, while the network strand governed the size sieving effect. From these results, we conclude that the polymer network with lower polymer volume fraction and smaller network strand is better in terms of size separation. The homogeneous polymer network is vital for understanding of particles’ dynamics in polymer network and a promising material for high-performance size separation.
The present study details facile synthesis of hollow Cu2O nanospheres decorated with Ag nanoparticles using a simple surfactant technique for enhanced photocatalytic activity. The morphology and structure is studied via XRD and SEM. Cu2O hollow nanospheres with a diameter of 500-800 nm were synthesized via Ostwald ripening using CuSO4 aqueous solution. The catalytic activity of Cu2O is studied in the presence of UV and visible light using Methyl Orange (MO) as a model pollutant. Ag decorated Cu2O particles showed a 49% increase in photocatalytic activity over the undecorated Cu2O. The improved photocatalytic activity is achieved by surface plasmon resonance effects in the silver nanoparticles, allowing utilization of the lower energy portion of the solar spectrum.
Topology optimization is a systematic, computational approach to the design of structure, defined as the layout of materials (and pores) across a domain. Typically employed at the component-level scale, topology optimization is increasingly being used to design the architecture of high performance materials. The resulting design problem is posed as an optimization problem with governing unit cell and upscaling mechanics embedded in the formulation, and solved with formal mathematical programming. This paper will describe recent advances in topology optimization, including incorporation of manufacturing processes and objectives governed by nonlinear mechanics and multiple physics, and demonstrate their application to the design of cellular materials. Optimized material architectures are shown to (computationally) approach theoretical bounds when available, and can be used to generate estimations of bounds when such bounds are unknown.
In the new DR-A in-situ diffusion experiment at Mont Terri, a perturbation (replacement of the initial synthetic porewater in the borehole with a high-salinity solution) has been induced to study the effects on solute transport and retention, and more importantly, to test the predictive capability of reactive transport codes. Reactive transport modeling is being performed by different teams (IDAEA-CSIC, PSI, Univ. Bern, Univ. British Columbia, Lawrence Berkeley Natl. Lab.). Initial modeling results using the CrunchFlow code and focusing on Cs+ behavior are reported here.
We present a new approach to prepare Transmission Electron Microscopy (TEM) nanowire (NW) samples that addresses the core drawbacks of conventional techniques, which are based on mechanical polishing. The proposed method is time efficient and uses XeF2 isotropic and selective dry etching of Si to remove the host substrate from the NWs, after their embedding into a poly(methyl-methacrylate) (PMMA) matrix. Scanning electron microscopy (SEM) data suggest that NWs were grown through the gaps between the parasitic layer islands and that the stems are in direct contact with the Si substrate. This technique does not adversely affect the NWs and offers a convenient means of transferring the GaAs NWs onto other surfaces for post-process TEM analysis. It also offers excellent potential to facilitate their integration into device fabrication via a bottom-up approach, using the PMMA layer as a transfer medium.
In this work, we report the synthesis of all-conjugated donor-acceptor block copolymers via a externally initiated Kumada catalyst-transfer polycondensation (KCTP) method. In the first step, electron acceptor blocks, poly(naphthalene diimide)s (PNDIs), were prepared via the Stille coupling polycondensation. Then, P3HT blocks were polymerized by KCTP initiated by Ni(COD)2 activated PNDI complexes. Therefore, a series of ABA (P3HTs were initiated from both ends of PNDI) and AB-type (P3HT was initiated from one end of PNDI) block copolymers were successfully synthesized. Before fabrication of all-polymer solar cells, the morphologies and crystalline behaviors of the block copolymers were extensively investigated as a function of thermal annealing and the main chain composition of PNDI block. As a control, the crystalline behaviors of the physical blends of P3HT and PNDIs were also reported. Finally, all-polymer solar cells were fabricated by using the block copolymers as the single active component or as surfactants. A PCE of 0.11 % with Voc=0.46 V, Jsc=0.50 mA/cm2, and FF=0.46 was recorded by using the donor-acceptor all-conjugated block copolymer as the single active component.
The paper reports on the fabrication of electrical isolation for planar AlGaN/GaN high electron mobility transistor using Al double-implantation. The implantation was performed using Al+ ions with energies of 800 keV and 300 keV with doses of 1.5×1013 ion/cm2 and 1×1013 ion/cm2, respectively. Electrical measurements have shown that after implantation the sheet resistance was 1.8×1011 Ω/□ and increased to 1.17×1014 Ω/□ and 3.29×1012 Ω/□ after annealing at 400°C and 600°C respectively. Annealing at 800°C decreased the sheet resistance to 1.38×108 Ω/□. Characterization by XRD, Raman and photoluminescence spectroscopy give evidence that implantation damages the crystal lattice, yielding insulating properties. It has been demonstrated that the isolation is stable up to 600°C.
A hierarchy of nanostructured-ZnO was fabricated on the electrospun nanofibers by atomic layer deposition (ALD) and hydrothermal growth, subsequently. Firstly, we produced poly(acrylonitrile) (PAN) nanofibers via electrospinning, then ALD process provided a highly uniform and conformal coating of polycrystalline ZnO with a precise control on the thickness (50 nm). In the last step, this ZnO coating depicting dominant oxygen vacancies and significant grain boundaries was used as a seed on which single crystalline ZnO nanoneedles (average diameter and length of ∼25 nm and ∼600 nm, respectively) with high optical quality were hydrothermally grown. The detailed morphological and structural studies were performed on the resulting nanofibers, and the photocatalytic activity (PCA) was tested with reference to the degradation of methylene blue. The results of PCA were discussed in conjunction with photoluminescence response. The nanoneedle structures supported the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. The enhanced PCA, structural stability and reusability of the PAN/ZnO nanoneedles indicated that this hierarchical structure is a potential candidate for waste water treatment.
Scanning probe microscopy, having the capability of nano-positioning and nanomanipulation, enables the characterization of material properties at a very small scale. In our previous work, the investigation of localized electrochemical reactions in Si3N4-TiC ceramic nanocomposites had been demonstrated using a single conductive scanning probe in a scanning impedance microscope (SIM). The results have provided experimental evidence that links the relations among microstructural heterogeneity, electrochemical property, and sintering behavior of spark plasma sintered ceramics. This single-probe SIM measurement gave through-body electrochemical information of specific surface feature of interest; however, the characterization of across-surface material properties in nanoscale is still much desired and unavailable.
To further investigate the heterogeneity of materials, we have designed and developed a dual-electrode scanning probe (DESP), which is capable of localized electrochemical characterization across the surface of a material. These probes were designed based on computer simulation and iterations, and fabricated using common semiconductor processing techniques. The span of two probes (electrodes) in our first prototypes was 10∼15 microns, which can be further reduced with optimized parameters. The DESP probes have been evaluated on Si3N4-TiC nanocomposites to demonstrate their functionality in topography scanning and in-situ impedance measurement. The impedance spectroscopy revealed two distinct impedance patterns for measurements across TiC-rich and Si3N4-rich surface regions. The design, fabrication, and evaluation of DESP were discussed in addition to the analysis of Si3N4-TiC nanocomposites.
Metal nanoparticle–decorated graphene oxides are promising materials for use in various optoelectronic applications because of their unique plasmonic properties. In this paper, a simple, environmentally friendly method for the synthesis of gold nanoparticle–decorated graphene oxide that can be used to improve the efficiency of organic photovoltaic devices (OPVs) is reported. Here, the amino acid glycine is empolyed as an environmentally friendly reducing reagent for the reduction of gold ions in the graphene oxide solutions. Furthermore, these nanocomposites are empolyed as the anode buffer layer in OPVs to trigger surface plasmonic resonance, which improved the efficiency of the OPVs. The results indicate that such nanomaterials appear to have great potential for application in OPVs.
The thermoluminiscent properties of MEH-PPV and MDMO-PPV conjugated polymers were studied in order to verify if they are suitable for use as TL dosimeter. The dose response that was analyzed cover the wide dose range 0.34-5.44 kGy. The measured glow curves show complex structures which were evaluated with kinetic parameters based on the MO (Mix Order) model together with the CGCD (Computerized Glow Curve Deconvolution) homemade program which is useful to understand the mechanisms responsible for TL emission.
Polysilsesquioxane passivation layers were used to passivate bottom gate a-InGaZnO (a-IGZO) thin film transistors (TFT). The a-IGZO TFTs passivated with polysilsesquioxane showed highly stable behavior during positive bias stress, negative bias stress, and negative bias illumination stress. A voltage threshold shift of up to 0.1 V, less than -0.1 V and -2.3 V for positive bias stress, negative bias stress, and negative bias illumination stress, respectively. We also report the effect of reactive ion etching (RIE) on the electrical characteristics of a-InGaZnO (a-IGZO) thin-film transistors (TFT) passivated with the polysilsesquioxane-based passivation layers. We show how post-annealing treatment using two different atmosphere conditions: under O2 ambient and combination of N2 and O2 ambient (20% O2), can be performed to recover the initial characteristics. Furthermore, we present a highly stable novel polysilsesquioxane photosensitive passivation material that can be used to completely circumvent the reactive ion etching effects.