Alpha Shape Analysis (ASA) Framework for Post- Clustering Property Determination in Atom Probe Tomographic Data.

While application of clustering algorithms to atom probe tomography data have enabled quantification of solute clusters in terms of number density, size, and subcomposition there exist other properties (e.g., volume, surface area, and composition) that are better determined by defining an interface between the cluster and the surrounding matrix. The limitation in composition results from an ion selection step where the expected matrix ion types are omitted from the cluster search algorithm to enhance the contrast between the matrix and cluster and to reduce the complexity of the search. Previously, composition determination within solute clusters has utilized a secondary envelopment and erosion step on top of conventional methods such as maximum separation. In this work, we present a novel stochastic method that combines the particle identification fidelity of a conventional clustering algorithm with the analytical flexibility of mesh-based approaches through the generation of alpha shapes for each identified cluster. The corresponding mesh accounts for concave components of the clusters and determines the volume and surface area of the clusters; additionally, the mesh boundary is utilized to update the total composition according to the internal ions.

Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals.

Large, freestanding membranes with remarkably high elastic modulus (>10 GPa) have been fabricated through the self-assembly of ligand-stabilized inorganic nanocrystals, even though these nanocrystals are connected only by soft organic ligands (e.g., dodecanethiol or DNA) that are not cross-linked or entangled. Recent developments in the synthesis of polymer-grafted nanocrystals have greatly expanded the library of accessible superlattice architectures, which allows superlattice mechanical behavior to be linked to specific structural features. Here, colloidal self-assembly is used to organize polystyrene-grafted Au nanocrystals at a fluid interface to form ordered solids with sub-10-nm periodic features. Thin-film buckling and nanoindentation are used to evaluate the mechanical behavior of polymer-grafted nanocrystal superlattices while exploring the role of polymer structural conformation, nanocrystal packing, and superlattice dimensions. Superlattices containing 3-20 vol % Au are found to have an elastic modulus of ∼6-19 GPa, and hardness of ∼120-170 MPa. We find that rapidly self-assembled superlattices have the highest elastic modulus, despite containing significant structural defects. Polymer extension, interdigitation, and grafting density are determined to be critical parameters that govern superlattice elastic and plastic deformation.

The Application of the OPTICS Algorithm to Cluster Analysis in Atom Probe Tomography Data.

Atom probe tomography (APT) is a powerful technique to characterize buried three-dimensional nanostructures in a variety of materials. Accurate characterization of those nanometer-scale clusters and precipitates is of great scientific significance to understand the structure-property relationships and the microstructural evolution. The current widely used cluster analysis method, a variant of the density-based spatial clustering of applications with noise algorithm, can only accurately extract clusters of the same atomic density, neglecting several experimental realities, such as density variations within and between clusters and the nonuniformity of the atomic density in the APT reconstruction itself (e.g., crystallographic poles and other field evaporation artifacts). This clustering method relies heavily on multiple input parameters, but ideal selection of those parameters is challenging and oftentimes ambiguous. In this study, we utilize a well-known cluster analysis algorithm, called ordering points to identify the clustering structures, and an automatic cluster extraction algorithm to analyze clusters of varying atomic density in APT data. This approach requires only one free parameter, and other inputs can be estimated or bounded based on physical parameters, such as the lattice parameter and solute concentration. The effectiveness of this method is demonstrated by application to several small-scale model datasets and a real APT dataset obtained from an oxide-dispersion strengthened ferritic alloy specimen.

Corona discharge plasma for green de-inking of inkjet printer ink.

This work features a new corona discharge plasma technology for de-inking yellow, blue, and red colors on various papers. This work was developed to minimize the chemical and environmental impacts of de-inking processes. A nonchemical contribution, operating at room temperature and atmospheric pressure, reduces the environmental impact of the process. The deinkability factor (DEMLab) values for all papers are determined with the optimal assessment results provided by a 36-mm variation gap at 2-min (blue) and 10-min (yellow and red) plasma exposure times, followed by applied voltages of 20 kV (yellow), 16 kV (blue), and 20 kV (red). The corona discharge plasma led to 48.58% (yellow printed paper), 64.11% (blue printed paper), and 41.11% (red printed paper) deinkability without altering the physical properties of the paper itself. The change in the tensile strength for the plasma-exposed paper was relatively little, less than 10%, compared to that of common recycling. The tensile strength of the untreated white paper was 5065 ± 487.44 N/mm2, and that of the plasma-treated printed paper was 4593 ± 248.47 N/mm2. It appears that there is little impact on the physicochemical properties of paper induced by the corona plasma treatment during the de-inking process.

Enhanced cold plasma hydrogenation with glycerol as hydrogen source for production of trans-fat-free margarine.

The quest for better nutritious foods has encouraged novel scientific investigations to find trans-fat reduction methods. This research proposes an innovative approach for the production of healthier trans-fat-free margarine from palm oil by the use of dielectric barrier discharge (DBD) plasma technology with glycerol serving as the principal source of hydrogen. The effectiveness of DBD plasma in hydrogenating palm olein was investigated. By employing a methodical series of experiments and thorough analytical approaches, examination of the saturated fatty acid conversion experienced its iodine value (IV) reduction from 67.16 ± 0.70 to 31.61 ± 1.10 under the optimal process parameters of 1 L min-1 He flow rate, 35 W plasma discharge power, 10 mm gap size, ambient initial temperature, and 12 h reaction time with solid texture. According to the method for producing trans-fat-free margarine in the absence of a catalyst and H2 gas, the hydrogenation rate of the prepared mixture of palm olein-glycerol was remarkably improved; the trans-fat content in the produced product was zero; the efficacy of incorporating cis- and trans-isomerization was lowered, and the method has a promising industrial application prospect.

Helium implantation effects on the compressive response of Cu nanopillars.

A fabrication methodology for 120 nm-diameter, <111>-oriented single crystalline Cu nanopillars which are uniformly implanted with helium is described. Uniaxial compression experiments reveal that their yield strength is 30% higher than that of their unimplanted counterparts. This study sheds light on the fundamental understanding of the deformation mechanism of irradiated metallic nanocrystals, and has important implications for the interplay between irradiation-induced defects and the external sample dimensions in the nanoscale.

Highly effective removal of perfluorooctanoic acid (PFOA) in water with DBD-plasma-enhanced rice husks.

Adsorption is regarded as an efficient method to eliminate per- and polyfluoroalkyl substances from an aqueous solution. In the present investigation, an adsorbent based on rice husks (RHs) was successfully prepared by phosphoric acid (PA) activation and dielectric barrier discharge (DBD) plasma treatment, and it was used to adsorb perfluorooctanoic acid (PFOA) from water. The electrodes employed in the experiment were planar type. This research investigated RH surface properties and adsorption capacity before and after modification using DBD plasma. The results revealed that the He-O2 plasma modification introduced oxygen-containing functional groups and increased the PFOA removal efficiency. Increasing the oxygen content and total gas flow rate to 30 vol.% and 1.5 L/min, respectively, with 10 min of RH plasma treatment time at 100 W plasma discharge power enhanced the PFOA removal efficiency to 92.0%, while non-treated RH showed the removal efficiency of only 46.4%. The removal efficiency of the solution increased to 96.7% upon adjusting the pH to 4. The adsorption equilibrium isotherms fitted the Langmuir model, and the adsorption kinetic followed the pseudo-second-order model. The maximum adsorption capacity was 565 mg/g when the Langmuir isotherm model was applied.

A free-standing lithium phosphorus oxynitride thin film electrolyte promotes uniformly dense lithium metal deposition with no external pressure.

Lithium phosphorus oxynitride (LiPON) is an amorphous solid electrolyte that has been extensively studied over the last three decades. Despite the promise of pairing it with various electrode materials, LiPON's rigidity and air sensitivity set limitations to understanding its intrinsic properties. Here we report a methodology to synthesize LiPON in a free-standing form that manifests remarkable flexibility and a Young's modulus of ∼33 GPa. We use solid-state nuclear magnetic resonance and differential scanning calorimetry to quantitatively reveal the chemistry of the Li/LiPON interface and the presence of a well-defined LiPON glass-transition temperature of 207 °C. Combining interfacial stress and a gold seeding layer, our free-standing LiPON shows a uniformly dense deposition of lithium metal without the aid of external pressure. This free-standing LiPON film offers opportunities to study fundamental properties of LiPON for interface engineering for solid-state batteries.

Iron-rich microstructure records of high temperature multi-component silicate melt behavior in nuclear fallout.

Above-ground nuclear explosions that interact with the surface of the earth entrain materials from the surrounding environment, influencing the resulting physical and chemical evolution of the fireball, which can affect the final chemical phase and mobility of hazardous radionuclides that are dispersed in the environment as fallout particles. The interaction of iron with a nuclear explosion is of specific interest due to the potential for iron to act as a redox buffer and because of the likelihood of significant masses of metals to be present in urban environments. We investigated fallout from a historic surface interacting nuclear explosion conducted on a steel tower and report the discovery of widespread and diverse iron-rich micro-structures preserved within the samples, including crystalline dendrites and micron-scale iron-rich spheres with liquid immiscibility textures. We assert these micro-structures reflect local redox conditions and cooling rates and can inform interpretation of high temperature events, enabling new insights into fireball condensation physics and chemistry when metals from the local environment (i.e. structural steel) are vaporized or entrained. These observations also significantly expand the availability of silicate immiscibility datasets applicable to rapidly quenched systems such as meteorite impact melt glass.

Low-cost alternative biodiesel production apparatus based on household food blender for continuous biodiesel production for small communities.

Fatty acid methyl esters (FAMEs) are sustainable biofuel that can alleviate high oil costs and environmental impacts of petroleum-based fuel. A modified 1200 W high-efficiency food blender was employed for continuous transesterification of various refined vegetable oils and waste cooking oil (WCO) using sodium hydroxide as a homogeneous catalyst. The following factors have been investigated on their effects on FAME yield: baffles, reaction volume, total reactant flow rate, methanol-oil molar ratio, catalyst concentration and reaction temperature. Results indicated that the optimal conditions were: 2000 mL reaction volume, 50 mL/min total flow rate, 1% and 1.25% catalyst concentration for refined palm oil and WCO, respectively, 6:1 methanol-to-oil molar ratio and 62-63 °C, obtaining yield efficiency over 96.5% FAME yield of 21.14 × 10-4 g/J (for palm oil) and 19.39 × 10-4 g/J (for WCO). All the properties of produced FAMEs meet the EN 14214 and ASTM D6751 standards. The modified household food blender could be a practical and low-cost alternative biodiesel production apparatus for continuous biodiesel production for small communities in remote areas.

Chemical manipulation of hydrogen induced high p-type and n-type conductivity in Ga2O3.

Advancement of optoelectronic and high-power devices is tied to the development of wide band gap materials with excellent transport properties. However, bipolar doping (n-type and p-type doping) and realizing high carrier density while maintaining good mobility have been big challenges in wide band gap materials. Here P-type and n-type conductivity was introduced in ß-Ga2O3, an ultra-wide band gap oxide, by controlling hydrogen incorporation in the lattice without further doping. Hydrogen induced a 9-order of magnitude increase of n-type conductivity with donor ionization energy of 20 meV and resistivity of 10-4 Ω.cm. The conductivity was switched to p-type with acceptor ionization energy of 42 meV by altering hydrogen incorporation in the lattice. Density functional theory calculations were used to examine hydrogen location in the Ga2O3 lattice and identified a new donor type as the source of this remarkable n-type conductivity. Positron annihilation spectroscopy measurements confirm this finding and the interpretation of the experimental results. This work illustrates a new approach that allows a tunable and reversible way of modifying the conductivity of semiconductors and it is expected to have profound implications on semiconductor field. At the same time, it demonstrates for the first time p-type and remarkable n-type conductivity in Ga2O3 which should usher in the development of Ga2O3 devices and advance optoelectronics and high-power devices.

Fabrication and thermo-mechanical behavior of ultra-fine porous copper.

Porous materials with ligament sizes in the submicrometer to nanometer regime have a high potential for future applications such as catalysts, actuators, or radiation tolerant materials, which require properties like high strength-to-weight ratio, high surface-to-volume ratio, or large interface density as for radiation tolerance. The objective of this work was to manufacture ultra-fine porous copper, to determine the thermo-mechanical properties, and to elucidate the deformation behavior at room as well as elevated temperatures via nanoindentation. The experimental approach for manufacturing the foam structures used high pressure torsion, subsequent heat treatments, and selective dissolution. Nanoindentation at different temperatures was successfully conducted on the ultra-fine porous copper, showing a room temperature hardness of 220 MPa. During high temperature experiments, oxidation of the copper occurred due to the high surface area. A model, taking into account the mechanical properties of the copper oxides formed during the test, to describe the measured mechanical properties in dependence on the proceeding oxidation was developed. The strain rate sensitivity of the copper foam at room temperature was ∼0.03 and strongly correlated with the strain rate sensitivity of ultra-fine grained bulk copper. Although oxidation occurred near the surface, the rate-controlling process was still the deformation of the underlying copper. An increase in the strain rate sensitivity was observed, comparably to that of ultra-fine-grained copper, which can be linked to thermally activated processes at grain boundaries. Important insights into the effects of oxidation on the deformation behavior were obtained by assessing the activation volume. Oxidation of the ultra-fine porous copper foam, thereby hindering dislocations to exit to the surface, resulted in a pronounced reduction of the apparent activation volume from ~800 to ~50 b3, as also typical for ultra-fine grained materials.