Layered transition metal dichalcogenides (TMDs) represent a diverse, emerging source of two-dimensional (2D) nanostructures with broad application in optoelectronics and energy. Chemical functionalization has evolved into a powerful tool to tailor properties of these 2D TMDs; however, functionalization strategies have been largely limited to the metallic 1T-polytype. The work herein illustrates that 2H-semiconducting liquid-exfoliated tungsten disulfide (WS2) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl3). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl3 is preferentially reduced on multi-layer WS2 and resulting large Au aggregates are easily separated from the colloidal dispersion by simple centrifugation. This process may be exploited to enrich the dispersions in laterally large, monolayer nanosheets. It is proposed that thiol groups at edges and defects sides reduce the AuCl3 to Au0 and are in turn oxidized to disulfides. Optical emission, i.e. photoluminescence, of the monolayers remained pristine, while the electrocatalytic activity towards the hydrogen evolution reaction is significantly improved. Taken together, these improvements in functionalization, fabrication, and catalytic activity represent an important advance in the study of these emerging 2D nanostructures.

Natural graphite can be exfoliated into thin films by trapping it at the interface between water and heptane [S. J Woltornist, A. J. Oyer, J-M. Y. Carrillo, A.V. Dobrynin, and D.H. Adamson, ACS Nano 7, 7062 (2013)]. In this work, we add functional elements into these graphitic thin films by introducing additives into the water phase prior to exfoliation. We report the successful incorporation of ZnO nanoparticles thereby enabling the composite films to act as effective ultraviolet photodetectors. In a similar manner, integration of silver nanowires is achieved, which results in an enhancement of the electrical conductivity of graphite.

Zeolite and cellulose-acetate nanocomposites were fabricated in this study using a combination of melt blending and solution mixing. The nanocomposites were optimized for heavy metal adsorption using spiked lead and cadmium solutions. Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy and Powder X-Ray diffraction crystallography were used for physical characterization. Fourier Transform Infrared spectra showed a reduction of the hydroxyl peak for cellulose acetate and that of the residual silanol group for zeolites symbolizing bonding during nanocomposite formation. Scanning Electron Microscope results showed an increase in voids with zeolite loading in the nanocomposites, a useful characteristic of good adsorbents. Powder X-ray diffraction crystallography results showed a reduction in 2 theta values for the nanocomposites due to penetration of the polymer into the silicate lattice e.g. zeolite 2 theta peak at 7.44° reduced to 7.09° in the nanocomposites signifying an increase in crystal lattice d- spacing from 1.188 nm to 1.247 nm. The nanocomposites adsorbed a maximum of 97.20% lead ions and 85.06% cadmium ions from solution.

Atomistic simulations are employed to investigate the dynamical behavior of atoms in cubic silicon carbide (SiC) following a 5 keV radiation knock. Specifically, we have computed the time-resolved van Hove self-correlation function, Gs(r,t), separately for the silicon and carbon sub-lattices. Our goal is to probe the early radiation damage mechanisms using a dynamical methodology. The simulation results show that the carbon atoms engage in a dynamic hopping mechanism as the system recovers from the radiation knock. The silicon atoms, however, exhibit a strikingly different behaviour: the time variation of 4πr2Gs(r,t) indicates a dynamic tension between the crystalline and disordered regions of the Si sub-lattice. The power-law tail of the 4πr2Gs(r,t) correlation for silicon atoms suggests a scale-free self-organized critical (SOC) state – a possible precursor to the collapse of the Si sub-lattice.

The room-temperature switching effect is of great interest for many applications, such as smart buildings, sensors, thermal energy storage and automatic temperature control. In this paper, we report a room-temperature switchable carbon nanotube (CNT)/hexadecane composites. Electrical conductivity, thermal conductivity and permittivity of the CNT/hexadecane composites can be regulated around 18°C and the maximal switching ratio reaches 5 orders of magnitude, 3 times and 106.4, respectively. The switching behavior of composites is caused by rearrangement of the carbon nanotube fillers in hexadecane matrix during liquid-solid phase transition. It is found that surface modification is necessary to improve dispersion stability. Effects of filler properties on switching behaviour are also discussed.

The production of biodiesel by the esterification of oleic acid, as an example of free fatty acid (FFA), was explored by using a new solid acid catalyst derived from lignin, a highly abundant low-cost biomass material. The catalyst was synthesized from lignin-derived carbon fiber by straightforward sulfonation and contains 1.86 mmol/g of sulfonic acid (-SO3H) groups. The catalyst was characterized by a variety of techniques including PXRD, TGA, TPD-MS, SEM, and XPS to understand the surface chemistry and the result of sulfonation. It was found that the sulfonated lignin-derived carbon fiber (CF-SO3H) catalyst was very efficient at esterifying oleic acid at 80 oC in 4 hours, with 10 wt. % catalyst (in terms of oleic acid content) and at a 10:1 molar ratio of methanol: oleic acid with a yield of 92%. Furthermore, the catalyst can be reused with no significant loss in activity after 4 cycles. Hence, synthesizing solid acid catalysts from lignin-derived carbon fiber affords a novel strategy for producing biodiesel via ‘green chemistry’.

In the present study, we analyze the influence of temperature and active layer thickness on the electrical properties of electroluminescent devices comprising a polymeric conductive blend (poly(3,4 ethylenedioxythiophene):polystyrene sulfonate, PEDOT:PSS), an inorganic electroluminescent material (manganese doped zinc orthosilicate, Zn2SiO4:Mn) and an organosilicon material (3-glicidoxypropyltrimethoxysilane, GPTMS), manufactured at different weight ratios of the component materials. The devices were obtained by depositing the active layer by drop-casting onto ITO-coated (RF-sputtering) glass substrates and thermally evaporating gold top electrodes in high vacuum. The results show that 90 wt% Zn2SiO4:Mn is required to observe high electroluminescence from the fabricated devices and that the optimum performance (turn-on voltage of 33 V, luminous efficacy of 24 cd/A and maximum luminance of almost 2000 cd/m2) was achieve for a (9.5/0.5/90) (GPTMS/PEDOT:PSS/Zn2SiO4:Mn) weight ratio. The device turn-on voltage found to be as proportional to the thickness of the active layer, indicating that the electroluminescence occurs by a field-effect mechanism. The temperature variation in the 100-300 K range allowed us to develop a theoretical model for the device operation, where the charge carrier transport in the active layer is well described by the variable range hopping model, with luminous efficacy nearby independent of the temperature.

In this study, AlGaN/GaN MIS-HEMTs with a p-GaN cap layer and ALD deposited Al2O3 gate insulator were fabricated. Devices with two different thicknesses of p-GaN cap layers were investigated and compared. AlGaN/GaN MIS-HEMT with an 8-nm p-GaN cap showed a better DC characteristics than device with a 5-nm p-GaN cap. The drain current of 662.9 mA/mm, a high on/off current ratio of 2.67×109 and a breakdown voltage of 672 V were measured in device with an 8-nm p-GaN cap. In addition, lateral leakage current was investigated by using adjacent MIS gate structures with a separation of 3 μm to investigate the leakage current.

Deposition of size-selected copper and silver nanoparticles (NPs) on polymers using cluster beam technique is studied. It is shown that ratio of particle embedment in the film can be controlled by simple thermal annealing. Combining electron beam lithography, cluster beam deposition, and heat treatment allows to form specific patterns (arrays) of metal NPs on polymer films. Plasticity and flexibility of polymer host and specific properties added by coinage metal NPs open a way for different applications of such composite materials, in particular, for the formation of plasmonic structures with required configurations which can be applied for wave-guiding, resonators, in sensor technologies, and surface enhanced Raman scattering.

Vanadium Pentoxide (V2O5) has been identified as a potential cathode material owning to its high specific capacity, theoretically, 441 mAh g-1 for 3Li+ ions insertion/extraction. However, the intrinsic drawbacks of V2O5, i.e. structural instability and poor electronic and ionic conductivity, greatly inhibit its application as a cathode. Here, we report a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal reaction to synthesize V2O5 nanoclusters. Unique aggregated fiber structure was obtained after annealing. To achieve a porous structure and increase the conductivity, nitrogen-doped Graphene (NG) suspended in ethylene glycol was added to the reaction mixture. The obtained spherical V2O5 nanoparticles and NG sheets were randomly dispersed in the matrix of the V2O5 spheres. As a cathode material for lithium-ion batteries, the V2O5/NG hybrids demonstrate better rate performance compared to the bundle-like V2O5 fibers, delivering higher specific capacity of ∼ 300 and 150 mAh g-1 at a rate of C/10 and 5C, respectively. The enhanced performance in lithium storage are attributed to the synergistic effect of the nanostructured V2O5/NG composites.

Atomic force microscopy (AFM) and nanoindentation were used to characterize poly (methyl methacrylate) (PMMA) films with a wide distribution of pores. Pores with diameters ranging from tens of nanometers to few micrometers were measured by AFM and cross-section scanning electron microscopy (SEM). Atomic force acoustic microscopy (AFAM) mapping of the elastic modulus were correlated with the samples topography and pore distribution. The elastic moduli of the samples were additionally measured by nanoindentation.

Density Functional Theory (DFT) calculations study of Cu doped {0001} and {01-12} surfaces of hematite for enhanced water splitting have been carried out. The doping was restricted to planes in the vicinity of the surface, specifically from the top most layers to the third inner layer of Fe atoms. Thermodynamic stabilities were evaluated based on surface energies and formation energies. The evaluation of thermodynamic stabilities (negative formation energy values) shows that the systems are thermodynamically stable which suggest that they can be synthesized in the laboratory under favorable conditions. Doping on the top most layer yields the energetically most favorable structure. The calculated charge density difference plots showed the concentration of charge mainly at the top of the surface (termination region), and this charge depleted from the Cu atom to the surrounding Fe and O atoms. This phenomenon (concentration of charge at the top of the surface) is likely to reduce the distance moved by the charge carriers, decrease in charge recombination leading to facile transfer of charge to the adsorbate and, suggesting improved photoelectrochemical water oxidation activity of hematite. The analysis of electron electronic structure reveals that Cu doped surface systems does not only decrease the band gap but also leads to the correct conduction band alignment for direct water splitting without external bias voltage.

We have developed Anti- Sievert® concrete, which is a concrete reinforced shielding function as a building material that shields the influence from radioactive materials and its radiation. Cement, water, aggregate, sand material, Anti- Sievert® # 210, Anti- Sievert® # 216 formulation was optimized as those materials constituting Anti- Sievert® concrete. As a result, we realized shielding concrete with high fluidity to realize construction suitability by concrete pump[1]. Anti- Sievert® concrete has a shielding function of about 3 times as compared with ordinary concrete with respect to X ray (100 kV), and shows strength of more than 50 N/mm2. The durability characteristics against nuclear explosion using Anti-Sievert® concrete were simulated and reported in this paper.

Liquid crystal polymers (LCP’s) comprise a class of materials that derive desirable, but anisotropic, engineering properties from long-range molecular ordering. The ability to model the polymer texture is essential to the design of manufacturing processes for isotropic material production. Previous efforts to model LCP directionality have been primarily restricted to structured grids and simple geometries that demonstrate the underlying theory, but fall short of simulating realistic manufacturing geometries. In this investigation, a practical methodology is proposed to simulate the director field in full-scale melt-processing domains and wide-angle x-ray scattering (WAXS) is used to experimentally validate modeling results. It is shown that the model generates good agreement with experimental measurements of both the orientation state and degree of order.

One of the goals of soft robotics is the ability to interface with the human body. Traditionally, silicone materials have dominated the field of soft robotics. In order to shift to materials that are more compatible with the body, developments will have to be made into biodegradable and biocompatible soft robots. This investigation focused on developing gummy actuators which are biodegradable, edible, and tasty. Creating biodegradable and edible actuators can be both sold as an interactive candy product and also inform the design of implantable soft robotic devices. First, commercially available gelatin-based candies were recast into pneumatic actuators utilizing molds. Edible robotic devices were pneumatically actuated repeatedly (up to n=8 actuations) using a 150 psi power inflator. To improve upon the properties of actuators formed from commercially available candy, a novel gelatin-based formulation, termed the “Fordmula” was also developed and used to create functional actuators. To investigate the mechanics and functionality of the recast gummy material and the Fordmula, compression testing and biodegradation studies were performed. Mechanical compression tests showed that recast gummy materials had similar properties to commercially available candies and at low strain had similar behavior to traditional silicone materials. Degradation studies showed that actuation was possible within 15 minutes in a biologically relevant solution followed by complete dissolution of the actuator afterwards. A taste test with elementary aged children demonstrated the fun, edible, and educational appeal of the candy actuators. Edible actuator development was an entry and winning submission in the High School Division of the Soft Robotics Toolkit Design Competition hosted by Harvard University. Demonstration of edible soft robotic actuators created by middle and high school aged students shows the applicability of the Soft Robotics Toolkit for K12 STEM education.

Inkjet printing, of the researched techniques for printing of hydrogels, gives perhaps the best potential control over the shape and composition of the final hydrogel. It is, however, fundamentally limited by the low viscosity of the printed ink, which means that crosslinking of the hydrogel must take place after printing. This can be particularly problematic for hydrogels as the slow diffusion of the crosslinking species through the gel results in very slow vertical printing speeds, leading to dehydration of the gel and (if simultaneously deposited) cell death. Previous attempts to overcome this limitation have involved the sequential printing of alternating layers to reduce the diffusion distance of reactive species. In this work we demonstrate an alternative approach where the crosslinker and gelator are printed so that they collide with each other before impinging upon the substrate, thereby facilitating hydrogel synthesis and patterning in a single step. Using a model system based upon sodium alginate and calcium chloride a series of 3D structures are demonstrated, with vertical printing speeds significantly faster than previous work. The droplet collision is shown to increase advective mixing before impact, reducing the time taken for gelation to occur, and improving definition of printed patterns. With the facile addition of more printing inks, this approach also enables spatially varied composition of the hydrogel, and work towards this will be discussed.

Zinc borate has long been used as a protector for wood products due to its fungicide, insecticide and flame retardant properties. In this initial study, its capacity as a flame retardant when applied to Eucalyptus grandis wood is evaluated; micronized zinc borate, synthesized from zinc oxide and boric acid in our laboratory was used. The methodology used in the study is the use of the Vandersall tunnel, which allowed analyzing parameters such as the flame spread, the carbonization index, the carbonization area and the wood weight loss. The results show a remarkable improvement in these parameters after the application of micronized zinc borate. For the longest fire exposure time, the percentage decrease of each evaluated parameter is, for tangential and radial plane respectively: 31.27-43.00% for flame spread, 36.66-40.86% for carbonization area, 33.01-52.49% for carbonization index and 19.86-57.80% for mass loss.

Polymer composites of Polylactic acid (PLA) and poly-ε-caprolactone (PCL), containing small amounts of titanium oxide (TiO2) were developed for biomedical applications. These composite materials were prepared, and then printed using Fused Deposition Modeling (FDM). 3D printed structures were characterized to determine their mechanical properties and biocompatibility. DSC analysis yielded useful information regarding the immiscibility of the different polymers, and it was observed that the particles of TiO2 improved the stability of the polymers. The ultimate tensile strength and the fracture strain increased by adding TiO2 as a filler, resulting in values of approximately 45 MPa and 5.5 % elongation. The printed composites show excellent in vitro biocompatibility including cell proliferation and adhesion, and are therefore promising candidates to be used in the biomedical field for bone replacement procedures, due to their properties similar to those of cancellous bone.

T91 ferritic/martensitic (F/M) steel is an expected structural material candidate for Gen IV liquid lead-bismuth cooled nuclear reactors. However, molten lead-bismuth eutectic alloy (mLBE) often causes liquid-metal embrittlement (LME) of F/M steels. Although prior austenite grain boundaries and martensite block boundaries were reported to be preferential sites for LME, the mechanism of LME in a T91/LBE couple is yet to be comprehensively understood. In this paper, the effect of mLBE on T91 steel was investigated using micropillar compression tests. mLBE corrosion was found to cause a significant decrease in yield stress. The micropillar made from mLBE-corroded specimen was significantly sheared along high angle boundaries. In addition, EDS analysis demonstrated the presence of Pb/Bi at these high angle boundaries.

An efficient enzymatic route for the synthesis of conducting oligomer of substituted aniline complexed with poly(sodium 4-styrenesulfonate) is presented. This polyelectrolyte assisted horseradish peroxidase catalyzed oligomerization of ortho-toluidine provides a route to synthesize water-soluble, highly conductive oligomers under acidic conditions. The UV-Vis, FTIR, thin film conductivity, molecular weight assessment and modeling studies of the oligomer/polymer complex indicate the presence of a thermally stable and electroactive oligomer with extended conjugation that was not present in similar conductive polymers (e.g. PANI). Moreover, the use of water-soluble templates provide a unique combination of properties such as high conductivity and processability. The same procedure was also implemented for the polymerization of 2,6-xylidine: however, the reaction did not occur suggesting a much more complex stereo-specificity of the enzymatic polymerization. Modeling studies were used to explain this behavior. The conductive poly(ortho-toluidine) can be used in chemiresistive sensors for the detection of humidity.