Anisotropic phase-separated morphology of polymer blends directed by electrically pre-oriented clay platelets.

We describe a general pathway to prepare an anisotropic phase-separated polystyrene (PS) - poly(vinyl methyl ether) (PVME) blend morphology by using electrically pre-orientated clay platelets. The clay platelets were oriented in a PS/PVME blend by means of an externally applied AC electric field while the blend is in one phase. Following orientation step, phase separation of the blends was induced by a temperature jump above their lower critical solution temperature (LCST) in the presence of the oriented clay platelets. In this process, an early stage co-continuous PS/PVME morphology coarsened and turned anisotropic phase-separated morphology parallel to the direction defined by clay planes oriented by AC electric field. The degree of anisotropy of PS/PVME phase-separated morphology was characterized by image analysis and that was found to be linearly proportional to the degree of orientation of clay platelets obtained by a 2D Wide Angle X-ray Scattering (WAXS). Transmission Electron Microscope (TEM) image of the blend morphology revealed that clay platelets oriented to AC field direction were located in a PVME phase. The electrically ordered column structures of clay platelets in the PVME phase yielded anisotropic PS diffusion during the phase separation. This process provides a unique new way to develop directionally organized phase-separated morphology from partially miscible binary blends using nanoparticles in combination with an external electric field.

Core-Shell Type Ionic Liquid/Metal Organic Framework Composite: An Exceptionally High CO2/CH4 Selectivity.

Here, we present a new concept of a core-shell type ionic liquid/metal organic framework (IL/MOF) composite. A hydrophilic IL, 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide, [HEMIM][DCA], was deposited on a hydrophobic zeolitic imidazolate framework, ZIF-8. The composite exhibited approximately 5.7 times higher CO2 uptake and 45 times higher CO2/CH4 selectivity at 1 mbar and 25 °C compared to the parent MOF. Characterization showed that IL molecules deposited on the external surface of the MOF, forming a core (MOF)-shell (IL) type material, in which IL acts as a smart gate for the guest molecules.

A Discovery of Strong Metal-Support Bonding in Nanoengineered Au-Fe3O4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy.

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous "strong metal-support bonding" between gold nanoparticles and "nano-engineered" Fe3O4 substrates by in situ microscopy. During in situ vacuum annealing of Au-Fe3O4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe3O4 on Au nanoparticles, the gold nanoparticles transform into the gold thin films and wet the surface of nano-Fe3O4, as the surface reduction of nano-Fe3O4 proceeds. This phenomenon results from a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe3O4 and the extremely strong adhesion between Au and the reduced Fe3O4. This strong metal-support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and ultimately for the development of improved catalysts and functional nanostructures.

Highly Stable Bimetallic AuIr/TiO2 Catalyst: Physical Origins of the Intrinsic High Stability against Sintering.

It has been a long-lived research topic in the field of heterogeneous catalysts to find a way of stabilizing supported gold catalyst against sintering. Herein, we report highly stable AuIr bimetallic nanoparticles on TiO2 synthesized by sequential deposition-precipitation. To reveal the physical origin of the high stability of AuIr/TiO2, we used aberration-corrected scanning transmission electron microscopy (STEM), STEM-tomography, and density functional theory (DFT) calculations. Three-dimensional structures of AuIr/TiO2 obtained by STEM-tomography indicate that AuIr nanoparticles on TiO2 have intrinsically lower free energy and less driving force for sintering than Au nanoparticles. DFT calculations on segregation behavior of AuIr slabs on TiO2 showed that the presence of Ir near the TiO2 surface increases the adhesion energy of the bimetallic slabs to the TiO2 and the attractive interactions between Ir and TiO2 lead to higher stability of AuIr nanoparticles as compared to Au nanoparticles.

Macromolecular structural dynamics visualized by pulsed dose control in 4D electron microscopy.

Macromolecular conformation dynamics, which span a wide range of time scales, are fundamental to the understanding of properties and functions of their structures. Here, we report direct imaging of structural dynamics of helical macromolecules over the time scales of conformational dynamics (ns to subsecond) by means of four-dimensional (4D) electron microscopy in the single-pulse and stroboscopic modes. With temporally controlled electron dosage, both diffraction and real-space images are obtained without irreversible radiation damage. In this way, the order-disorder transition is revealed for the organic chain polymer. Through a series of equilibrium-temperature and temperature-jump dependencies, it is shown that the metastable structures and entropy of conformations can be mapped in the nonequilibrium region of a "funnel-like" free-energy landscape. The T-jump is introduced through a substrate (a "hot plate" type arrangement) because only the substrate is made to absorb the pulsed energy. These results illustrate the promise of ultrafast 4D imaging for other applications in the study of polymer physics as well as in the visualization of biological phenomena.

A Comparative Study of Gallium-, Xenon-, and Helium-Focused Ion Beams for the Milling of GaN.

The milling profiles of single-crystal gallium nitride (GaN) when subjected to focused ion beams (FIBs) using gallium (Ga), xenon (Xe), and helium (He) ion sources were investigated. An experimental analysis via annular dark-field scanning transmission electron microscopy (ADF-STEM) and high-resolution transmission electron microscopy (HRTEM) revealed that Ga-FIB milling yields trenches with higher aspect ratios compared to Xe-FIB milling for the selected ion beam parameters (30 kV, 42 pA), while He-FIB induces local lattice disorder. Molecular dynamics (MD) simulations were employed to investigate the milling process, confirming that probe size critically influences trench aspect ratios. Interestingly, the MD simulations also showed that Xe-FIB generates higher aspect ratios than Ga-FIB with the same probe size, indicating that Xe-FIB could also be an effective option for nanoscale patterning. Atomic defects such as vacancies and interstitials in GaN from He-FIB milling were suggested by the MD simulations, supporting the lattice disorder observed via HRTEM. This combined experimental and simulation approach has enhanced our understanding of FIB milling dynamics and will benefit the fabrication of nanostructures via the FIB technique.

4D scanning transmission ultrafast electron microscopy: Single-particle imaging and spectroscopy.

We report the development of 4D scanning transmission ultrafast electron microscopy (ST-UEM). The method was demonstrated in the imaging of silver nanowires and gold nanoparticles. For the wire, the mechanical motion and shape morphological dynamics were imaged, and from the images we obtained the resonance frequency and the dephasing time of the motion. Moreover, we demonstrate here the simultaneous acquisition of dark-field images and electron energy loss spectra from a single gold nanoparticle, which is not possible with conventional methods. The local probing capabilities of ST-UEM open new avenues for probing dynamic processes, from single isolated to embedded nanostructures, without being affected by the heterogeneous processes of ensemble-averaged dynamics. Such methodology promises to have wide-ranging applications in materials science and in single-particle biological imaging.

Introduction of Rare-Earth Oxide Nanoparticles in CNT-Based Nanocomposites for Improved Detection of Underlying CNT Network.

Epoxy resins for adhesive and structural applications are widely employed by various industries. The introduction of high aspect ratio nanometric conductive fillers, i.e., carbon nanotubes, are well studied and are known to improve the electrical properties of the bulk material by orders of magnitude. This improved electrical conductivity has made carbon nanotube-based nanocomposites an attractive material for applications where their weight savings are at a premium. However, the analytical methods for validating carbon nanotube (CNT) nanofiller dispersion and for assuring that the properties they induce extend to the entire volume are destructive and inhibited by poor resolution between matrix and tube bundles. Herein, rare-earth oxide nanoparticles are synthesized on CNT walls for the purpose of increasing the contrast between their network and the surrounding matrix when studied by imaging techniques, alleviating these issues. The adherence of the synthesized nanoparticles to the CNT walls is documented via transmission electron microscopy. The crystalline phases generated during the various fabrication steps are determined using X-ray diffraction. Deep ultraviolet-induced fluorescence of the Eu:Y2O3-CNT nanostructures is verified. The impacts to nanocomposite electrical properties resulting from dopant introduction are characterized. The scanning electron microscopy imaging of CNT pulp and nanocomposites fabricated from untreated CNTs and Eu:Y2O3-CNTs are compared, resulting in improved contrast and detection of CNT bundles. The micro-CT scans of composites with similar results are presented for discussion.

Quality of graphite target for biological/biomedical/environmental applications of 14C-accelerator mass spectrometry.

Catalytic graphitization for (14)C-accelerator mass spectrometry ((14)C-AMS) produced various forms of elemental carbon. Our high-throughput Zn reduction method (C/Fe = 1:5, 500 degrees C, 3 h) produced the AMS target of graphite-coated iron powder (GCIP), a mix of nongraphitic carbon and Fe(3)C. Crystallinity of the AMS targets of GCIP (nongraphitic carbon) was increased to turbostratic carbon by raising the C/Fe ratio from 1:5 to 1:1 and the graphitization temperature from 500 to 585 degrees C. The AMS target of GCIP containing turbostratic carbon had a large isotopic fractionation and a low AMS ion current. The AMS target of GCIP containing turbostratic carbon also yielded less accurate/precise (14)C-AMS measurements because of the lower graphitization yield and lower thermal conductivity that were caused by the higher C/Fe ratio of 1:1. On the other hand, the AMS target of GCIP containing nongraphitic carbon had higher graphitization yield and better thermal conductivity over the AMS target of GCIP containing turbostratic carbon due to optimal surface area provided by the iron powder. Finally, graphitization yield and thermal conductivity were stronger determinants (over graphite crystallinity) for accurate/precise/high-throughput biological, biomedical, and environmental (14)C-AMS applications such as absorption, distribution, metabolism, elimination (ADME), and physiologically based pharmacokinetics (PBPK) of nutrients, drugs, phytochemicals, and environmental chemicals.

Investigation of laser-induced inter-welding between Au and Ag nanoparticles and the plasmonic properties of welded dimers.

Noble metallic nanoparticles with unique plasmonic properties are useful in a variety of applications including bio-imaging, sensing, cancer therapy, etc. The properties of metallic nanoparticles can be tuned in multiple ways, among which laser welding is a highly efficient method. In this study, laser-induced inter-welding of Ag-Au nanoparticle (NP) dimers was investigated using in situ transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX). For the first time, the welding process was directly visualized. The structural and compositional evolution of Ag-Au dimers was studied in detail, and several typical nanostructures formed during the welding process, including two types of core-shell structures, were discovered. Based on these observations, we proposed a complete mechanism explaining how welding proceeds under the influence of a laser. Finite difference time domain (FDTD) simulations demonstrated that the plasmonic properties of welded Ag-Au dimers were different from those of pure Au-Au or Ag-Ag dimers and can be tuned by forming shells, alloying or changing the size ratio of Ag and Au NPs.

Secondary signal imaging (SSI) electron tomography (SSI-ET): A new three-dimensional metrology for mesoscale specimens in transmission electron microscope.

We have demonstrated a new electron tomography technique utilizing the secondary signals (secondary electrons and backscattered electrons) for ultra thick (a few µm) specimens. The Monte Carlo electron scattering simulations reveal that the amount of backscattered electrons generated by 200 and 300keV incident electrons is a monotonic function of the sample thickness and this causes the thickness contrast satisfying the projection requirement for the tomographic reconstruction. Additional contribution of the secondary electrons emitted from the edges of the specimens enhances the visibility of the surface features. The acquired SSI tilt series of the specimen having mesoscopic dimensions are successfully reconstructed verifying that this new technique, so called the secondary signal imaging electron tomography (SSI-ET), can directly be utilized for 3D structural analysis of mesoscale structures.

Migration of Single Iridium Atoms and Tri-iridium Clusters on MgO Surfaces: Aberration-Corrected STEM Imaging and Ab Initio Calculations.

To address the challenge of fast, direct atomic-scale visualization of the migration of atoms and clusters on surfaces, we used aberration-corrected scanning transmission electron microscopy (STEM) with high scan speeds (as little as ∼0.1 s per frame) to visualize the migration of (1) a heavy atom (Ir) on the surface of a support consisting of light atoms, MgO(100), and (2) an Ir3 cluster on MgO(110). Sequential Z-contrast images elucidate the surface transport mechanisms. Density functional theory (DFT) calculations provided estimates of the migration energy barriers and binding energies of the iridium species to the surfaces. The results show how the combination of fast-scan STEM and DFT calculations allow visualization and fundamental understanding of surface migration phenomena pertaining to supported catalysts and other materials.

Plasmonic enhanced emissions from cubic NaYF(4):Yb: Er/Tm nanophosphors.

A metal shell was used in this study to provide significant enhancement of the up-converted emission from cubic NaYF(4) nanoparticles, creating a valuable composite material for labeling in biology and other applications - use of the cubic form of the material obviates the need to undertake a high temperature transformation to the naturally more efficient hexagonal phase. The NaYF(4) matrix contained ytterbium sensitizer and an Erbium (Er) or Thulium (Tm) activator. The particle sizes of the as-synthesized nanoparticles were in the range of 20-40 nm with a gold shell thickness of 4-8 nm. The gold shell was macroscopically amorphous. The synthesis method was based on a citrate chelation. In this approach, we exploited the ability of the citrate ion to act as a reductant and stabilizer. Confining the citrate ion reductant on the nanophosphor surface rather than in the solution was critical to the gold shell formation. The plasmonic shell enhanced the up-conversion emission of Tm from visible and near-infrared regions by up to a factor of 8, in addition to imparting a visible color arising from the plasmon absorption of the gold shell. The up-conversion enhancement observed with Tm and Er were different for similar gold coverages, with local crystal field changes as a possible route to enhance up-conversion emission from high symmetry structural hosts. These novel up-converting nanophosphor particles combine the phosphor and features of a gold shell, providing a unique platform for many biological imaging and labeling applications.

Direct imaging of single metal atoms and clusters in the pores of dealuminated HY zeolite.

Zeolites are aluminosilicate materials that contain regular three-dimensional arrays of molecular-scale pores, and they can act as hosts for catalytically active metal clusters. The catalytic properties of such zeolites depend on the sizes and shapes of the clusters, and also on the location of the clusters within the pores. Transmission electron microscopy has been used to image single atoms and nanoclusters on surfaces, but the damage caused by the electron beam has made it difficult to image zeolites. Here, we show that aberration-corrected scanning transmission electron microscopy can be used to determine the locations of individual metal atoms and nanoclusters within the pores of a zeolite. We imaged the active sites of iridium catalysts anchored in dealuminated HY zeolite crystals, determined their locations and approximate distance from the crystal surface, and deduced a possible cluster formation mechanism.

Towards full-structure determination of bimetallic nanoparticles with an aberration-corrected electron microscope.

To fully understand the properties of functional nanostructures such as catalytic nanoclusters, it is necessary to know the positions of all the atoms in the nanostructure. The catalytic properties of metal nanoclusters can often be improved by the addition of a second metal, but little is known about the role of the different metals in these bimetallic catalysts, or about their interactions with each other and the support material. Here we show that aberration-corrected scanning transmission electron microscopy of supported rhodium-iridium clusters, combined with dynamic multislice image simulations, can identify individual atoms, map the full structure, and determine changes in the positions of metal atoms in sequential images. This approach could help in the development of new and improved catalysts and other functional nanostructures.

Site-isolated iridium complexes on MgO powder: individual Ir atoms imaged by scanning transmission electron microscopy.

Iridium complexes were synthesized on MgO powder by adsorption of Ir(C(2)H(4))(2)(acac) [acac = acetonylacetonate]; images determined by aberration-corrected scanning transmission electron microscopy show individual Ir atoms, demonstrating that the supported complexes were site-isolated.

Nanoclusters of gold on a high-area support: almost uniform nanoclusters imaged by scanning transmission electron microscopy.

Highly dispersed supported gold offers unprecedented catalytic properties. Determination of the dependence of the catalytic properties on the gold nanocluster size requires the preparation of size-controlled gold nanoclusters on support surfaces with a high degree of uniformity. Starting from site-isolated mononuclear gold complexes on high-area MgO, we demonstrate the preparation of gold clusters consisting of <10 atoms. These samples have been imaged with atomic resolution by aberration-corrected scanning transmission electron microscopy. The images show that treatment of the supported mononuclear complexes at 318 K in flowing helium caused aggregation of the gold into clusters of 2-6 atoms, present with unconverted individual site-isolated mononuclear gold species and in the absence of any larger nanoparticles. Treatment of the sample at a higher temperature (373 K) in flowing helium resulted in the formation of gold clusters with diameters of 0.58 +/- 0.15 nm (containing roughly 10 Au atoms), again in the absence of larger nanoparticles. Upon exposure of the supported nanoclusters to the electron beam, they underwent aggregation to gold clusters approximately 1 nm in average diameter, as shown in consecutive STEM images.