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Bimetallic nanoparticles (NPs), particularly Au/Pd and Au/Pt, have attracted extensive attention due to their wide-spread application in catalysis, optoelectronics and energy recuperation.[1] Here we have attempted the fabrication of Au/Pt and Au/Pd bimetallic NPs by an energy-efficient eco-friendly microwave methodology. The microwave-assisted reactions enable considerably large product yields over conventional colloidal methods due to (a) almost two-fold increased reaction kinetics, (b) localized superheating at reaction sites and rapid rise of initial temperature.[2] Au NPs (sizes 20 ± 3 nm) are fabricated in the first step followed by the reduction of [PdCl2(NH3)2] or [K2PtCl6]in tetraethylene glycol at 180 ºC for 2 min. Controlling and understanding the atomic structure and elemental distributions of these NPs are crucial for their optimized performances. So, we address the fundamental question of the most likely arrangement of Au and Pd or Pt atoms in these bimetallic NPs prepared under similar conditions by complementary characterizations using UV-Vis spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The UV-Vis spectroscopy reveals the formation of an alloy shell. The extent of depression of the plasmon peak of Au and its blue-shift reveals substantial deposition of Pd atoms on an Au core and significant alloying in comparison to Au/Pt NPs. XRD reveals the gradual shift of the diffraction peak from the position of Au to the position of Pd or Pt with change in composition. XRD supports the formation of a thick alloy shell in these NPs. However, the TEM images reveal a very interesting result. With increase in Pt concentration, the size of the dispersed NPs decreases from 20 ± 3 nm to about 16 nm (± 1 nm) and there is evolution of a bimodal particle size distribution with small particles about 1-2 nm diameters. On the contrary, with increasing Pd concentration, the particle size of the dispersed particles increases to about 32 nm (± 1 nm). This discrepancy of particle size evolution for the two systems arises due to the differences in surface energies (Pt > Pd > Au atoms). Pt atoms tend to diffuse towards the core with the formation of Au nano-islands which eventually segregates leading to a reduction in particle size and bimodal distribution. At higher concentration of Pt, Pt and Au atoms tend to nucleate separately also contribute to the bimodal distribution. While for Au/Pd NPs, we have an Au core with an alloyed shell having higher Pd concentration. This is further supported by experimental evidence by selective etching and dissolution of Au by potassium-iodide solution. Furthermore, the Au/Pd bimetallic NPs are found to possess better catalytic activities in the reduction of 4-nitrophenol to 4-aminophenol than Au/Pt and monometallic NPs.
Undergraduate materials engineering students have difficulty conceptualizing the atomic-level processes responsible for plastic deformation. To aid in developing this conceptual understanding, interactive molecular dynamics (MD) simulations were introduced into the sophomore-level materials curriculum, integrating simulation with the traditional tensile testing laboratory. Students perform a tensile test using MD simulations on nanowire samples, and then compare these results with those from the physical tensile tests to develop a visual and more intuitive picture of plastic deformation of crystalline materials.
For nine years, an REU program placed over 200 undergraduate researchers at Northeastern University, the University of Massachusetts Lowell, and the University of New Hampshire through the NSF-funded Nanoscale Science and Engineering Center for High-rate Nanomanufacturing. The cross-university professional development program included university-based research skills, communication skills with the Boston Museum of Science, and a unique method for researcher evaluation of the societal impact of their decisions. This work presents the impacts of this research program as measured at program end, along with the career progress of the REU participants, recent interviews with REU participants, and reflections by REU program leaders.
Two-step growth method of low pressure chemical vapor deposition(LPCVD) process was employed to fabricate the ZnO:B-TCO film; For the first layer, the seed layer with a heavy doping concentration was deposited on the glass substrate, the film having higher deposition rate were then grown on the top of the first layer; It shows that the doping situations of the seed layer play an important role in electrical and optical performance of the whole ZnO:B-TCO layer, and the combination of this two properties is optimal when the doping ratio (B2H6/DEZ) was 0.4;
Architectural design research in next-generation building systems is transforming dynamic building envelope performance towards systems that not only meet the energy demands of buildings but also respond to occupant preferences for aesthetics, comfort and control. Although research provides tremendous potential for future systems, existing tools and methods of evaluation primarily focus on energy efficiency and continue to postpone human factors issues. In order to assess the architectural opportunities of nano- and micro-material innovations for building facades, new simulation methods are needed to predict and program their multifunctional performance capabilities, particularly in relationship to human interaction. This paper describes the construction of augmented reality simulations and preliminary experimental results of co-optimizing advanced building skin performance according to multiuser interaction and bioclimatic response. The strengths and limitations of the augmented reality simulations in relation to environmental performance and human interaction are presented. A discussion of ongoing work focuses on the integration of multiuser interactions and virtual reality techniques coupled with whole-building energy modeling methods.
Comprehensive characterization of materials suggests measuring their different properties for optimal use in technological applications and this task becomes more challenging as size of related structures decreases and their complexity increases. At smaller scales Atomic Force Microscopy (AFM) enables visualization of structures and quantitative measurements of their mechanical and electric properties. So far, several properties such as elastic modulus and work of adhesion, surface potential and dielectric permittivity can be extracted from the results obtained in various AFM modes. More complicated are the AFM experiments and their analysis in case of viscoelastic, piezoelectric and thermoelectric properties. Several examples of quantitative characterization of neat polymers will be given. In many cases the dissimilarity of the components’ properties is employed for their recognition in heterogeneous systems such as polymer blends, block copolymers and metal alloys. The confined geometries, which are common for small-scale structures, might restrict such identification and a combination of AFM with spectral methods such as Raman scattering will be helpful. Achievements and challenges of compositional mapping will be illustrated on several complex materials.
The present work reports on the fabrication, experimental and theoretical investigation of thermal conductivity (TC) and viscosity of ethylene glycol (EG) based nanofluids/microfluids (NFs/MFs) containing copper nanoparticles (Cu NPs) and copper microparticles (Cu MPs). Cu NPs (20-40 nm) and Cu MPs (0.5-1.5 μm) were dispersed in EG with particle concentration from 1 wt% to 3 wt% using powerful ultrasonic agitation, and to study the real impact of dispersed particles the use of surface modifier was avoided. The objectives were to study the effect of concentration and impact of size of Cu particles on thermo-physical properties, including thermal TC and viscosity, of EG based Cu NFs/MFs. The physicochemical properties of NPs/MPs and NFs/MFs were characterized by using various techniques. The experimental results exhibited higher TC of NFs and MFs than the EG base liquid. Moreover, Cu NFs displayed higher TC than MFs showing their potential for use in some heat transfer applications. Maxwell effective medium theory as well as Einstein law of viscosity was used to compare the experimental data with the predicted values for estimating the TC and viscosity of Cu NFs/MFs, respectively.
Optical components such as lenses, glass windows, and prisms are subject to Fresnel reflection due to the mismatch between the refractive indices of the air and glass. An optical interface layer, i.e., antireflection (AR) layer, is needed to eliminate this unwanted reflection at the air/glass interface. Nanostructured broadband and wide-angle AR structures have been developed using a scalable self-assembly process. Ultra-high performance of the nanostructured AR coatings has been demonstrated on various substrates such as quartz, sapphire, polymer, and other materials typically employed in optical lenses. AR coatings on polycarbonate lead to optical transmittance enhancement from approximately 90% to almost 100% for the entire visible, and part of the near-infrared (NIR), band. The AR coatings have also been demonstrated on curved surfaces. AR coatings on n-BK7 lenses enable ultra-high light transmittance for the entire visible, and most of the NIR, spectrum. Nanostructured oxide layers with step-graded index profiles, deposited onto the optical elements of an optical system, can significantly increase sensitivity, and hence improve the overall performance of the system.
The mechanical properties of stacked graphene sheets with varying number of layers are examined. The stacked sheets are assembled by manually combining single layer CVD-grown graphene monolayers, resulting in a turbostratic multilayer graphene with irregular layer spacings greater than crystalline graphite. Due to the presence of multiple layers, the material is analyzed as a plate rather than a membrane. Bending stiffness is determined via the deflection of micron-scale cantilevers, prepared using focused ion beam milling, while in-plane tensile stiffness is characterized through center-loading of edge-supported circular specimens. Computational modeling and established analytical solutions are used to extract material and structural property information, and benchmark measured properties relative to complementary results from indentation tests. Stacked, few-layer CVD-grown graphene retains an in-plane elastic modulus of 350N/m/layer (corresponding to 1.04 TPa for an inter-layer spacing of 0.335nm), suggesting good load-sharing between stacked layers. Width-normalized bending stiffness was unmeasurable for cantilevers of 1 and 3 layers, while cantilevers of 5 and 10 layers had values of 11,100nN·nm and 1.3×106nN·nm respectively.
Growth of GaN on Si(111) and Ge coated Si(111) using pulsed electron beam deposition (PED) process is reported. GaN was deposited on Si(111) and Ge/Si(111) at 600°C in an N2 environment without any surface pre-treatment such as pre-nitridation. X-ray diffraction confirmed that c-plane oriented GaN was grown. Photoluminescence showed near-band-edge emission, the intensity of which was improved with hydrogen passivation. Electrical characterization showed n-type conductivity with room temperature electron mobilities in the range of 300 cm2/V-sec.
In nature, biomolecules guide the formation of hierarchically-ordered, lightweight, inorganic-organic composites such as corals, shells, teeth and bones. M13 bacteriophage has been used to mimic bio-inspired material development due to its rigid, nanoscale rod-like morphology. Liquid-crystalline monolayers of genetically engineered phage have been used to template crystallization of thin layers of inorganic and metallic materials. We have created thin films composed of engineered M13 phage capable of binding inorganic components. We employed both a dip-cast and a drop-cast film fabrication method on both smooth and rough gold, silica and glass casting surfaces to create thin films and 3D structures of various degrees of hierarchical order. We have found the engineered M13 phage and the inorganic mineral significantly affected both film morphology and the mechanical properties of the film. Similarly, film fabrication parameters such as solution chemistry, temperature, and pulling speed affected film properties. Using a calcium phosphate biomineralized 4E phage, film thickness increased linearly with the number of layers/dips in the phage solution. The stiffness of these composites (Young's modulus) were >80 GPa for mineralized, multilayer films. These materials are an order of magnitude stiffer than the biological equivalent collagen. Stiffness, however, does not appear to increase in a multilayer film beyond a saturation point. Ultimately, we have developed a platform for phage-based bio-composites for developing high performance materials.
The influence of threading dislocations (TDs) on the dry thermal oxidation of c-plane gallium nitride (GaN) is investigated for oxidation temperatures above 800°C. The transformation of GaN to gallium oxide (Ga2O3) is preferably found at TDs and grain boundaries, showing enhanced vertical oxidation, compared to defect free surface sites. Therefore, the increase in surface roughness commonly obtained upon oxidation is explained by an inhomogeneous chemical reactivity associated with those crystal defects. Additionally, annealing in an N2 atmosphere showed that also decomposition is favored at such chemically reactive spots. Comparison between decomposition and oxidation suggests that at temperatures above 950°C, the Ga2O3 formation is supported by the decomposition of GaN and subsequent oxidation of the metallic gallium.
Increased demand for low cost energy storage options has expanded the scope of Na+ batteries considerably; and with the growing interest in Na-based chemistries, the importance of high voltage positive electrodes is quickly realized as the Na/Na+ redox introduces lower operating voltages as compared to Li/Li+ based electrochemical cells. The 4.7V LiMn1.5Ni0.5O4 spinel has exhibited considerable properties as a high voltage Li+ positive electrode, with a host structure (λ-Mn0.75Ni0.25O2) that may provide an analogous high voltage Na+ positive electrode. Structural and electrochemical properties of NaxMn1.56Ni0.44O4 and NaxMn2O4 are investigated for the first time[1] utilizing ex-situ, in-situ X-ray diffraction, and high-resolution electrochemical techniques to provide an insightful study of the Na+ insertion mechanism.
One approach to treating atrial fibrillation relies on freezing tissue of the heart wall. This surgical technology requires sub-millimeter spatial resolution when dynamically tracking the freezing of pulmonary vein; conventional techniques such as ultrasound lack the necessary precision. Here we use an electrothermal “3ω” method to track propagating freezing fronts in nearly real time. The heater line is excited with multiple frequencies simultaneously, and the freezing front detected as it passes through the various penetration depths due to the contrast between thermal conductivities on either side of the front. Comparison of water freezing experiments with video images further suggests the accuracy of the method. Analysis and experiments show how the uncertainty, time response, and measurement range depend on the frequencies and thermal conductivity contrast. Finally, the method is demonstrated on biological tissue as further proof of principle for medical applications.
Silicon nanocrystals are photoluminescent materials with a tremendous scope in various niche applications especially the generation of hybrid materials. Our approach for the preparation of stimuli responsive SiNC hybrid materials is based on the application of surface-initiated group-transfer polymerization. As a first step we used photografting of ethyleneglycol di(methacrylate). Then we impregnated remaining methyl acrylic surface groups with the catalyst Cp2YCH2TMS(thf). We performed polymerization studies regarding catalyst and diethyl vinylphosphonate (DEVP) concentrations, highlighting that surface grafting is dependent upon catalyst concentration and independent from added monomer amount. Furthermore, we successfully polymerized methyl methacrylate, dimethyl vinylphosphonate and diisopropyl vinylphosphonate from the SiNC surface.
Area-selective electroless deposition of gold nanostructures on a 6H-SiC substrate is demonstrated. Gold nanostructures selectively grow on a focused ion beam (FIB)-irradiated area on the 6H-SiC substrate when the substrate is exposed to a pure HAuCl4 aqueous solution. The nucleation of gold was more favorable on the Si face than on the C face. Quantitative evaluation of the amount of gold grown both on SiC and silicon is conducted to discuss the growth of gold, where silicon is a substrate we used in our previous study on this method. We reveal the mechanism of the growth of gold nanostructures as follows: Dangling bond defects formed in the FIB-irradiated area initiate the nucleation of gold by reducing Au ions in the solution at the surface. Once the SiC-gold or the silicon-gold boundary, which meets the Schottky contact condition, has formed, electrons in the non-FIB-irradiated region under/around the FIB-irradiated one also reduce Au ions on the gold surface through the boundary.