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Transparent films of platinum nanoparticles on graphene nanohybrids were synthesized in a two-step process. Reduction of homogeneously dispersed Pt precursor and graphene in water and solution coating/annealing afforded thin films with high catalytic performance as counter electrodes in dye-sensitized solar cells (DSSC). The requisite dispersant consisting of poly(oxyethylene)-(POE) segments and cyclic imide functionalities allowed the in-situ reduction of dihydrogen hexachloroplatinate by ethanol and the formation of nanohybrids of graphene-supported Pt nanoparticles at 4.0 nm diameter. Characterizations of polymeric dispersants by Fourier-transform infrared spectroscopy, thermogravimetric analysis, and nanohybrids by transmission electron microscope were performed. After screening various compositions of Pt/graphene, the nanohybrid film at the specific ratio of 5/1 by weight was fabricated into a counter electrode (CE) for DSSC by the solution casting method. The evaluation of cell performance demonstrated the most improved power conversion efficiency of 8.00%. This is significant achievement in comparison with 7.14% for the DSSC with the conventional platinum sputtered CE. Furthermore, the solution casting method allows the preparation of transparent CE films that are suitable for using as rear-illuminated DSSC. The approach was proven to be feasible by measuring the cell efficiency under rear light illumination. The power efficiency up to 7.01%, comparable to 8.00% by a normally front illumination, has been accomplished. In contrast, the rear illumination at merely 2.36% efficiency was obtained for the DSSC with sputtered platinum CE. Analyses of cyclic voltammetry, electrochemical impedance spectra were well correlated to the high efficiency of the performance caused by this nanohybrid film.
We have studied CuLi0.08Mg1.92 and determined that the compound reacts with hydrogen to form CuLi0.08Mg1.92H5 [1]. Additionally, we have proposed the compound as a negative electrode material which is the main purpose of the present study. Moreover, we have observed that the latter compound acts as a catalyst in the formation of MgH2, LiH, TiH2 [2] and hydrogen desorption. In this work, first principles and phonon calculations were performed in order to establish the reactions occurring at the negative electrode of a Li conversion battery in presence of CuLi0.08Mg1.92H5 and (Li) – solid solution of Mg in Li – approximately Li2Mg3. We have calculated the minimum theoretical specific capacity to be 1156 mAh/g (for an anode with 100% of CuLi0.08Mg1.92H5) and the △Eeq = 0.81 V (vs. Li+/Li) at 298 K. Furthermore, we have determined all the reactions occurring in the referred system and its sequence using Inelastic Incoherent Neutron Scattering (IINS) and X-Ray Diffraction (XRD).
The mechanical properties of ZnO nanowires are the “enabling factor” for piezotronic nanogenerators. Examining the size effects entail the determination of both elastic (i.e. the Young’s Modulus, E) and failure strength (e.g. fracture, fatigue, buckling, etc.) properties of ZnO nanostructures for nanogenerators. An investigation directed to both types of effects is presented here for the first time. On one hand the strength size effects are pointed out and discussed in the framework of a generalized Weibull framework that is set forward for ZnO NWs. On the other hand, the implications of the size effects on elasticity properties are discussed and quantified using numerical simulations. The results demonstrate that the stiffening of smaller NWs can adversely affect the performance in a non-negligible manner, suggesting that both mechanical size-effects have to be considered for design purposes.
In this study, the failure mechanisms of graphene under sliding are examined using atomistic simulations. A 6nm diameter diamond tip is slid (at a controlled normal load) over a graphene monolayer that is adhered to a semi-infinite silicon substrate. The impact of tip adhesion on the wear and frictional behavior of graphene is studied by comparing two diamond tips, one of which has been hydrogen-passivated and the other which is bare carbon. By contrasting the passivated and unpassivated tips, the interplay of adhesive and abrasive wear on the graphene membrane can also be compared. The results of this work indicate that chemical bonding between the tip and the graphene greatly exacerbates tearing in the graphene monolayer by plowing ahead of the indenter, causing material build-up and increasing effective contact area.
In this paper, we developed textile-based sensors for measuring vital signs. We fabricated conductive fiber made from organic conjugated polymers without the use of inorganic materials. While the tensile strength of pure poly-3,4-ethylenedioxythiophene/poly-4-styrene sulfonic acid (PEDOT/PSS) fiber was low, it was unsuitable to fabricate textile-based devices. To avoid this drawback, we examined the composite fibers composed of PEDOT/PSS and poly(vinyl alcohol) (PVA) to obtain good mechanical properties as well as a high electronic conductivity. PVA was used as a matrix component to connect colloidal PEDOT/PSS particles within the fibers. We succeeded continuous and uniform spinning from the mixed solution of PEDOT/PSS and PVA through the modified wet spinning process. Tensile strength of the composite fiber increased to twice that consisted only of PEDOT/PSS. In addition, the electric conductivity increased about three times by the combination with PVA. Textiles made of conductive fibers behaved as flexible electrodes for the detection of heartbeat.
We are interested in designing nanostructured biomaterials using nanoscopic building blocks such as functionalized nanotubes and lipid molecules. In our earlier work, we summarized the multiple control parameters which direct the equilibrium morphology of a specific class of nanostructured biomaterials. Individual lipid molecules were composed of a hydrophilic head group and two hydrophobic tails. A bare nanotube encompassed an ABA architecture, with a hydrophobic shaft (B) and two hydrophilic ends (A). We introduced hydrophilic hairs at one end of the tube to enable selective transport through the channel. The dimensions of the nanotube were set to minimize its hydrophobic mismatch with the lipid bilayer. We used a Molecular Dynamics-based mesoscopic simulation technique called Dissipative Particle Dynamics which simultaneously resolves the structure and dynamics of the nanoscopic building blocks and the hybrid aggregate. The amphiphilic lipids and functionalized nanotubes self-assembled into a stable hybrid vesicle or a bicelle in the presence of a hydrophilic solvent. We showed that the morphology of the hybrid structures was directed by factors such as the temperature, the rigidity of the lipid molecules, and the concentration of the nanotubes. Another type of hybrid nanostructured biomaterial could be multi-component lipid bilayers. In this paper, we present approaches to design hybrid nanostructured materials using multiple lipid species with different chemistries and molecular chain stiffness.
The preparation of site-specific atom-probe tomography (APT) samples containing localized features has become possible with the use of focused ion beams (FIBs). This technique was used to achieve the analysis of surface oxides and oxidized grain boundaries in this paper. Transmission electron microscopy (TEM), providing microstructural and chemical characterization of the same features, has also been used, revealing crucial additional information.
The study of grain boundary oxidation in stainless steels and nickel-based alloys is required in order to understand the mechanisms controlling stress corrosion cracking in nuclear reactors. Samples oxidized under simulated pressurized water reactor primary water conditions were used, and FIB lift-out TEM and APT specimens containing the same oxidized grain boundary were prepared and fully characterized. The results from both techniques were found fully consistent and complementary.
Chromium-rich spinel oxides grew at the surface and into the bulk material, along grain boundaries. Nickel was rejected from the oxides and accumulated ahead of the oxidation front. Lithium, which was present in small quantities in the aqueous environment during oxidation, was incorporated in the oxide. All phases were accurately quantified and the effect of different experimental parameters were analysed.
The paper presents the brief information on particular results of experimental studies dealing with the problems of properties of materials based on fibre-cement and fibre-concrete composites, which are being recently developed, tested and verified, to use them in the plated components of load-carrying structures of building constructions. The problems mentioned are solved in the co-operation with the company of the Research Institute of Building Materials Inc. (“VUSTAH a.s.”) at Brno city in the Czech Republic. The attention is paid to two basic types of material: (i) fibre-cement composite used for the slab components intended for vertical or horizontal building or technology structures, such as permanent shuttering of bridges, timber floor structures and slab flooring, the wall cladding of buildings and formwork of components in manufacturing plants of the concrete units; (ii) glass-fibre-concrete composite mainly intended for the building façade claddings, but also for the objects of daily use. The experimental verification has been mainly oriented to the investigation of physical-mechanical properties, like as the tensile-bending strength, as well as the corresponding modulus of elasticity.
As an important method for preparing ordered mesoporous polymer and carbon, organic template directed self-assembly is facing challenges because of the weak non-covalent interactions between the organic templates and the building blocks. Herein we developed a novel synthetic procedure based on a reactive template-induced self-assembly to construct ordered mesoporous framework. The aldehyde end-group of reactive template can react with the building blocks (i.e., resol) to form a stable covalent bond during the self-assembly process. This leads to an enhanced interaction between resol and template and thus achieves the formation of ordered mesostructure.
The growth mechanism of large-size domains in PbTiO3/SrTiO3 heteroepitaxial thin films was examined using annular bright field (ABF) – scanning transmission electron microscopy and geometric phase analysis (GPA). {101} domain walls surrounded 90° domains. The large 90° domain grows by the coalescence of the nano-size domains of less than 5 nm width. A strain map obtained from the GPA of ABF-STEM image showed that 90° domains interacted elastically and attractively with edge dislocations at PbTiO3/SrTiO3 interface through simple shear strain.
We fabricated MoS2 transistor adopting electric double layer (EDL) as gate dielectric. So far, EDL has realized p-type conducting MoS2 in addition to well-known n-type conduction showing ambipolar operation. In our study, field-effect superconducting transition of MoS2 was realized with maximum TC around 10 K. This TC is the highest not only within MoS2 compounds but also among whole TMDs. The highest TC discovered in this study lies in the carrier density region much smaller than chemically investigated region. Such compounds with small doping level have never been successfully synthesized by chemical method. Furthermore, by combining HfO2 (typical high-k material for FETs) gating with EDL gating, continuous control of carrier density, and thus quantum phase, was demonstrated. As a result, we successfully obtained the phase diagram of MoS2. Interestingly, the TC exhibits strong carrier density dependence, showing dome-shaped superconducting phase. Superconducting dome in other materials than cuprates has been reported only a few times in doped 2D semiconductors. Since FET charge accumulation is basically two dimensional, our result implies the existence of common mechanism for superconducting dome in 2D band insulators.
In order to explore the feasibility for preparing defined crosslinked particulate structures, oligo(ε-caprolactone) [oCL] derived microparticles (MPs) were crosslinked in non-molten, non-dissolved, i.e. solid state in aqueous suspension by applying a controlled regime with well-defined polymer network precursors either with or without photoinitiator. The MPs (diameter ∼ 40 μm) were prepared by an oil-in-water emulsion process from linear 2oCL or 4-arm star-shaped 4oCL with methacrylate end groups. Crosslinking was initiated by UV-laser irradiation (308 nm) at room temperature. Conversion of methacrylate was monitored by ATR-FTIR spectroscopy and crosslinking was confirmed by a lack of MP dissolution in dichloromethane. In a quantitative evaluation of swelling by dynamic light scattering, higher swelling ratios were detected for particles synthesized with photoinitiator. Wrinkled particle surfaces and distorted particle shapes were observed by light microscopy in the solvent-swollen state and by scanning electron microscopy after deswelling. This work indicated some limitations due to internal inhomogeneity of the MP, but particle crosslinking in solid state was generally possible and may be further improved by higher chain mobility during crosslinking.
This investigation describes preliminary results of in-situ analysis of zinc deposition within an ionic liquid electrolyte utilizing electrochemical atomic force microscopy (EC AFM). From the AFM analysis, the morphology of the zinc deposition was analyzed by quantifying the surface roughness using height-height correlation functions. These results will be used to analyze the scattering data obtained from zinc deposition analysis utilizing an electrochemical ultra-small angle x-ray scattering (EC USAXS). The goal of this research is to link the early nucleation and growth behavior to the formation of detrimental morphologies.
Results of investigation of X-ray sensors on the basis of GaAs compensated with chromium (HR GaAs) are presented in this work. HR GaAs material is shown to have the following physical parameters: the resistivity about 1GOhm*cm, the nonequilibrium charge carrier lifetime – hundreds of nanoseconds. Prototypes of microstrip and array HR GaAs sensors have been manufactured and tested. It is demonstrated that the sensors provide spatial resolution according to the pixel pitch and allow obtaining high quality X-ray images.
Crystal structure change with an applied electric field was investigated by Raman spectroscopy and X-ray diffraction (XRD) for the 1 μm-thick (100)/(001) one-axis oriented tetragonal Pb(Zr0.3Ti0.7)O3 films prepared on Pt-covered (100) Si substrates by chemical solution deposition technique. As-deposited films were under the strained condition in good agreement with the estimation from the thermal strain applied under the cooling process after the deposition from the Curie temperature to the room temperature. This strain was ascertained to be relaxed by an applied electric field in accompanying with the dramatic increase of the volume fraction of (001) orientation. These results demonstrate the importance of the crystal structure measurement not only as-deposited films, but also after applied electric field, such as after poling.
Polymers possessing antimicrobial activity have been used for self sterilization surfaces as well as agents for treating contaminated water. Cationic polymers based on quaternary ammonium or guanidine groups have shown high inherent antimicrobial activity where the activity is related to the disruption of the microorganism cell wall. A range of antimicrobial nanoparticles possessing active quaternary ammonium groups with one of the alkyl is a an octyl chain have been synthesized. These nanoparticles were incorporated in dental restoration compositions to form self sterile composites. Quaternary ammonium polyethyleneimine nanoparticles with N-octyl dimethyl residues, demonstrated high antibacterial effect.
The interface between a matrix and its reinforcement is critical to the final composite properties. There are different ways to enhance bonding between the reinforcing fiber and the matrix, based mainly on surface plasma treatments which usually decrease the fiber tensile strength. In this research, atomic layer deposition (ALD) was tested as a possible way to enhance the chemical bonding between the fiber and matrix in the hope that it would not effect the fiber tensile strength. Microbond tests were carried out to measure the effect of an ALD aluminum oxide (Al2O3) coating on the fiber/matrix interfacial shear strength, and the fiber tensile strength was measured in order to assess whether this treatment harms the fiber strength. The ultrahigh molecular weight polyethylene (UHMWPE) fibers that were coated by ALD with aluminum oxide (Al2O3) showed a significant increase in the interfacial shear strength without reducing the fibers’ ultimate tensile strength.
Most of polishing conditions are not consistent during the polishing process such as pressure, velocity, temperature, pad surface asperity and slurry flow which determine the CMP performance. Traditionally, these parameters are detected by various monitoring methods on CMP polisher. This study introduces a new concept of intelligent pad system with multiple sensors and peripheral devices such as memory, CPU, battery, transmitter and so on. The main functions of the intelligent pad are sensing the change of major parameters and data processing in real-time during the polishing process. The developed intelligent pad has nine points of embedded pressure sensor and makes data processing, saving, and transmitting in real-time. Experimentally, the intelligent pad system was evaluated to understand carrier behavior and pressure distribution. Finally, the analysis of pressure distribution using the intelligent pad turned out a useful method to understand the polishing head behavior and the polishing profile.