High-resolution Electron Microscopy Analysis Research Articles

Shortened carbon nanotubes and their influence on the electrical properties of polymer nanocomposites

Multi-wall carbon nanotubes of medium length (mCNTs) were aggressively tip-ultrasonicated to produce shortened and damaged carbon nanotubes (xCNTs). High-resolution electron microscopic analysis was performed to measure the dimensions of carbon nanotubes (CNTs). Thermo-gravimetric analysis and Raman spectroscopy were used to evaluate the damage in the sonicated CNTs. Short CNTs (sCNTs), in their pristine form (undamaged), were used for comparison with sonicated xCNTs. Good dispersion was achieved when CNTs were bath-ultrasonicated in epoxy resin. The electrical conductivities were measured for cured CNT/epoxy nanocomposites. Compared to shorter CNTs (xCNT and sCNT), mCNT lowered the percolation threshold of CNT/epoxy nanocomposites for electrical conductivity. While ultrasonically shortened xCNTs did give a percolation threshold similar to that of sCNT/epoxy nanocomposites, lower ultimate electrical conductivities were obtained for nanocomposites based on xCNTs due to the presence of structural defects.

XRD and HREM studies from the decomposition of icosahedral AlCuFe single-phase by high-energy ball milling

In this investigation the Al 64Cu 24Fe 12 alloy was melted in an induction furnace and solidified under normal casting conditions. In order to obtain the icosahedral phase (i-phase) in a single-phase region, the as-cast sample was subject to a heat treatment at 700 °C under argon atmosphere. Subsequently, the i-phase was milled for different times in order to evaluate phase stability under heavy deformation. X-ray diffraction (XRD) and high-resolution electron microscopy (HREM) analysis were conducted to the structural characterization of ball-milled powders. XRD results indicated a reduction in quasicrystal size during mechanical ball milling to about 30 h. HREM analysis revealed the presence of aperiodic nano-domains, for example, with apparent fivefold symmetry axis. Therefore, the i-phase remains stable over the first 30 h of ball-milling time. However, among 30–50 h of mechanical milling the i-phase transforms progressively into β-cubic phase.

New evidence on the nature of the metastable S″-phase on Al–Cu–Mg alloys

Results obtained from high resolution electron microscopy (HRTEM), the resultant fast Fourier transform (FFT) and the simulated electron diffraction patterns (SEDP) presented in this paper provide a better understanding that suggests that there is no S″-phase and that the effects attributed to S″ are explained by consideration of the various variants of the equilibrium S phase on Al–Cu–Mg based alloys (based only on HRTEM analysis). From the 12 orientation variants, only 3 orientations between the matrix and S-phase precipitates were taking into consideration in this study. It was found that the metastable S″-phase could be explained as an orientation variant of the equilibrium S-phase (Al 2CuMg). It is worth mentioning that the third variant has not been reported in the literature using HTREM, therefore, the incorporation of this variant in the analysis provides an alternative explanation for the experimental evidence previously used as support for the S″-phase.

Lead coprecipitation with iron oxyhydroxide nano-particles

Pb 2+ and Fe 3+ coprecipitation was studied with sorption edge measurements, desorption experiments, sorbent aging, High Resolution Transmission and Analytical Electron Microscopy (HR TEM–AEM), and geochemical modeling. Companion adsorption experiments were also conducted for comparison. The macroscopic chemical and near atomic scale HRTEM data supplemented our molecule scale analysis with EXAFS ( Kelly et al., 2008). Coprecipitation of Pb 2+ with ferric oxyhydroxides occurred at ∼pH 4 and is more efficient than adsorption in removing Pb 2+ from aqueous solutions at similar sorbate/sorbent ratios and pH. X-ray Diffraction (XRD) shows peaks of lepidocrocite and two additional broad peaks similar to fine particles of 2-line ferrihydrite (2LFh). HRTEM of the Pb–Fe coprecipitates shows a mixture of 2–6 nm diameter spheres and 8–20 by 200–300 nm needles, both uniformly distributed with Pb 2+. Geochemical modeling shows that surface complexation models fit the experimental data of low Pb:Fe ratios when a high site density is used. Desorption experiments show that more Pb 2+ was released from loaded sorbents collected from adsorption experiments than from Pb to Fe coprecipitates at dilute EDTA concentrations. Desorbed Pb 2+ versus dissolved Fe 3+ data show a linear relationship for coprecipitation (CPT) desorption experiments but a parabolic relationship for adsorption (ADS) experiments. Based on these results, we hypothesize that Pb 2+ was first adsorbed onto the nanometer-sized, metastable, iron oxyhydroxide polymers of 2LFh with domain size of 2–3 nm. As these nano-particles assembled into larger particles, some Pb 2+ was trapped in the iron oxyhydroxide structure and re-arranged to form solid solutions. Therefore, the CPT contact method produced more efficient removal of Pb 2+ than the adsorption contact method, and Pb 2+ bound in CPT solids represent a more stable sequestration of Pb 2+ in the environment than Pb 2+ adsorbed on iron oxyhydroxide surfaces.

Distribution of Microfossils Within Polymetallic Nodules: Biogenic Clusters Within Manganese Layers

Biomineralization is the process by which living organisms or organic matrices produced by them initiate and structure deposition of inorganic polymers/minerals. Deep-sea polymetallic nodules and crusts have recently been recognized as biominerals that are formed around bio-seeds; these deposits are of economic value. A detailed understanding of their formation will contribute to their sustainable exploitation in the future. Polymetallic nodules grow concentrically around discrete nuclei that have recently been described as bio-seeds formed from microorganisms, diatoms, or coccoliths. In the present study, polymetallic nodules from the Clarion-Clipperton Zone have been analyzed. It is described that the approximately 5-cm large polymetallic nodules are composed of micronodules (size of 100-450μm) that aggregated to nests (2-3mm). High-resolution scanning electron microscopy (HR-SEM) and high-resolution energy dispersive X-ray (HR-EDX) spectroscopic analyses revealed that the micronodules are composed of discrete layers of Mn and Fe. Imprints of microorganisms/microbe-like assemblies are found in the Mn-rich regions of the micronodules. HR-SEM/EDX analyses confirmed that these microorganisms are surrounded by a Mn-rich environment. These findings strongly suggest that those organisms acted as bio-seeds that allowed the deposition of Mn(IV) minerals which in turn helped Fe minerals to associate. Hence, these data support the concept that the growth of the polymetallic nodules starts as a biomineral and is completed by genuine mineralic depositions. It is expected that these data will contribute to the development of strategies for a sustainable exploitation of the polymetallic nodules.

Electron Microscopy of Cocatalyst Nanostructures on Semiconductor Photocatalysts

AbstractA thorough analytical electron microscopy investigation into the oxidized nickel cocatalyst structure on known photocatalytic materials NiTa2O6 and InTaO4 has been conducted. These photocatalyst materials have previously been reported in the literature to have activity in the splitting of water to form H2, and with the addition of a cocatalyst, such as NiO/Ni core shell nanoparticles, activity has been suggested to improve. Although important implications are placed on the effect of this cocatalyst, its structure has not previously been examined in detail. By using high resolution analytical transmission electron microscopy it has been determined that the structure is not as simple as suggested and, although a core shell metal/metal oxide structure is produced, in neither case is a perfect Ni/NiO composition obtained. In particular, in the case of the InTaO4 based material, the nominal NiO/Ni cocatalyst contains indium diffused into the nanoparticles from the photocatalyst support. The general implications of this result for the design of potential photocatalyst systems are discussed.

Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization

Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brust's two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand.

Cultivation‐independent characterization of ‘Candidatus Magnetobacterium bavaricum’ via ultrastructural, geochemical, ecological and metagenomic methods

'Candidatus Magnetobacterium bavaricum' is unusual among magnetotactic bacteria (MTB) in terms of cell size (8-10 µm long, 1.5-2 µm in diameter), cell architecture, magnetotactic behaviour and its distinct phylogenetic position in the deep-branching Nitrospira phylum. In the present study, improved magnetic enrichment techniques permitted high-resolution scanning electron microscopy and energy dispersive X-ray analysis, which revealed the intracellular organization of the magnetosome chains. Sulfur globule accumulation in the cytoplasm point towards a sulfur-oxidizing metabolism of 'Candidatus M. bavaricum'. Detailed analysis of 'Candidatus M. bavaricum' microhabitats revealed more complex distribution patterns than previously reported, with cells predominantly found in low oxygen concentration. No correlation to other geochemical parameters could be observed. In addition, the analysis of a metagenomic fosmid library revealed a 34 kb genomic fragment, which contains 33 genes, among them the complete rRNA gene operon of 'Candidatus M. bavaricum' as well as a gene encoding a putative type IV RubisCO large subunit.

Facile synthesis of mesophase pitch/exfoliated graphite nanoplatelets nanocomposite and its application as anode materials for lithium-ion batteries

Mesophase pitch (MP)/exfoliated graphite nanoplatelets (GNPs) nanocomposite has been prepared by an efficient method with an initiation of graphite intercalation compounds (GIC). X-ray diffraction, optical microscopy, high-resolution transmission electron microscopy and scanning electron microscopy analysis techniques are used to characterize the samples. It is observed that GIC has exfoliated completely into GNPs during the formation of MP/GNPs nanocomposite and the GNPs are distributed uniformly in MP matrix, which represent a conductive path for a movement of electrons throughout the composites. Electrochemical tests demonstrate that the carbonized MP/GNPs nanocomposite displays higher capacity and better cycle performance in comparison with the pure carbonized MP. It is concluded that such a large improvement of electrochemical performance within the nanocomposite may in general be related to the enhanced electronic conductivity, which is achieved by good dispersion of GNPs within MP matrix and formation of a 3D network of GNPs.

Critical Aspects of Alloying of Sintered Steels with Manganese

This study examines the sintering behavior and properties of Fe-0.8Mn-0.5C manganese powder metallurgy steels. The study focuses on the influence of mode of alloying—admixing using either high-purity electrolytic manganese or medium carbon ferromanganese as well as the fully prealloying of water-atomized powder. Three main aspects were studied during the whole sintering process—microstructure development, interparticle necks evolution, and changes in the behavior of manganese carrier particles during both heating and sintering stages. The prealloyed powder shows considerable improvement in carbon homogenization and interparticle neck development in comparison with admixed materials. The first indication of pearlite for the fully prealloyed material was registered at ~1013 K (740 °C) in comparison with ~1098 K (825 °C) in the case of the admixed systems. The negative effect of the oxidized residuals of manganese carrier particles and high microstructure inhomogeneity, which is a characteristic feature of admixed systems, is reflected in the lower values of the mechanical properties. The worst results in this respect were obtained for the system admixed with electrolytic manganese because of more intensive manganese sublimation and resulting oxidation at lower temperatures. According to the results of X-ray photoelectron spectroscopy and high-resolution scanning electron microscopy and energy dispersive X-ray analyses, the observed high brittleness of admixed materials is connected with intergranular decohesion failure associated with manganese oxide formation on the grain boundaries.

Growth mechanism of catalyst‐free [0001] GaN and AlN nanowires on Si by molecular beam epitaxy

AbstractReal‐time in‐situ X‐rays scattering experiments were performed to study the nucleation process of GaN nanowires grown by plasma‐assisted molecular beam epitaxy on AlN(0001)/Si(111). From the comparison between the case of nanowires and the case of GaN quantum dots, it is concluded that nanowire precursor islands are completely relaxed from the beginning. Next, based on high resolution electron microscopy analysis, it is demonstrated that relaxation of nanowire precursors is associated to formation of dislocations at the AlN/GaN interface, establishing that three‐dimensional islanding and plastic strain relaxation of GaN are two necessary conditions for nanowire growth. Along the same lines, we demonstrate that three‐dimensional islanding of AlN on SiO2 leads to formation of AlN nanowires with structural and optical properties characteristic of high quality relaxed material (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Property engineering in BaTiO3 films by stoichiometry control

BaTiO3 thin films were prepared on metallic foil substrates using chemical solution deposition. The impact of A to B site cation ratios on the phase assemblage and microstructural and dielectric properties was investigated by characterizing a sample set that includes stoichiometric BaTiO3 and 1, 2, 3, 4, and 5 mol% excess BaO. Each composition was subjected to a high-temperature anneal step with maximum dwell temperatures of 1000, 1100, and 1200 °C for 20 h. Excess barium concentrations greater than 3% lead to dramatic grain growth and average grain sizes exceeding 1 μm. Despite the large deviations from stoichiometry and the 20 h dwell time at temperature, x-ray diffraction, and high-resolution electron microscopy analysis were unable to detect secondary phases until films with 5% excess barium were annealed to 1200 °C. Thin films with 3% excess barium were prepared on copper substrates and annealed at 1060 °C, the practical limit for copper. This combination of BaO excess and annealing temperature produced an average lateral grain size of 0.8 μm and a room-temperature permittivity of 4000. This is in comparison to a permittivity of 1800 for stoichiometric material prepared using identical conditions. This work suggests metastable solubility of BaO in BaTiO3 that leads to enhanced grain growth and large permittivity values. This technique provides a new solid-state means of achieving grain growth in low thermal budget systems.

Elastic strain relaxation in GaN/AlN nanowire superlattice

The molecular-beam epitaxy growth of AlN/GaN nanowire superlattices has been studied by using a combination of in situ x-ray diffraction experiments, high-resolution electron-microscopy analysis and theoretical calculations performed in a valence force field approach. It is found that the nanowire superlattices are in elastic equilibrium, in contrast with the two-dimensional case but in line with the predicted increase in the critical thickness in the nanowire geometry.

Microstructure of high velocity oxy-fuel sprayed Ti2AlC coatings

The microstructure formation and phase transformations in Ti2AlC-rich coatings deposited by High Velocity Oxy-fuel spraying of Maxthal 211(A (R)) powders is presented. High resolution electron microscopy analysis, using both scanning and transmission electron microscopy with energy dispersive spectrometry and energy filtering, combined with X-ray diffraction reveals that the coatings consist of Ti2AlC grains surrounded by regions of very small TiC grains embedded in Ti (x) Al (y) . The composition of the Ti (x) Al (y) depends on its surrounding and varies with size and distribution of the adjacent TiC grains. Impact of spray parameters on coating microstructure is also discussed. Two spray parameters were varied; powder size distribution and flame power. They were found to greatly affect the coating microstructure. Increasing powder size and decreasing flame power increase the amount of Ti2AlC, but produces thinner coatings with lower cohesion. Larger powder size will also decrease oxygen incorporation.

Advanced microstructure diagnostics and interface analysis of modern materials by high-resolution analytical transmission electron microscopy

Advanced microstructure diagnostics and interface analysis of modern materials by high-resolution analytical transmission electron microscopy

Superparamagnetic cobalt-ferrite-modified carbon nanotubes using a facile method

Abstract Cobalt ferrite (CoFe 2 O 4 )/carbon nanotube (CNT) magnetic nanocomposites were synthesized by a facile solvothermal method. X-ray powder diffractometry (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), High-resolution electron microscopy (HRTEM) analyses demonstrate that cubic CoFe 2 O 4 nanoparticles were immobilized on the external surfaces of the CNTs. Vibrating sample magnetometer (VSM) measurements indicated that the nanocomposites at room temperature were superparamagnetic with a saturation magnetization of 29.6 emu g −1 .

HREM and EDS analysis of (La, M)TiO3 (M = Zn, Mn) prepared by M/Li ion exchange

High-resolution electron microscopy (HREM) and energy dispersive X-ray spectroscopy (EDS) studies of (La, M)TiO3 (M = Zn, Mn) prepared by M/Li ion exchange were performed to clarify the microscopic mechanism of ion-exchange reactions. At a macroscopic level, EDS analysis revealed that Zn and Mn atoms were homogeneously dispersed in matrix grains of (La, Zn)TiO3 and (La, Mn)TiO3 samples, respectively. EDS analysis also revealed that no segregation of Zn and Mn atoms was observed even in the vicinity of grain boundary regions. HREM and EDS analysis demonstrated that the microscopic mechanism of ion-exchange reactions was different by the ion-exchanged metals.

Lanthanum cobaltite nanoparticles using the polymeric precursor method

The present study reports the evolution of reactive lanthanum cobaltite nanoparticles obtained by a polymeric precursor route, using citric acid as chelating agent. The crystallization from amorphous precursor, particle growth and the formation of nanoparticle agglomerates at different calcination temperatures was carried out by conventional and high-resolution electron microscopy, electron diffraction and energy-dispersive X-ray analysis and Raman spectroscopy. Microstructure measurements were compared with X-ray diffraction and chemical analysis results. Electron diffraction, combined with TEM, was used to determine the proportion of amorphous phase. The presence of amorphous carbon during the decomposition of the amorphous precursor was analyzed by Raman spectroscopy. The coherent crystalline domain size and the particle size have been monitored by XRD and electron microscopy in order to determine the evolution of both crystal size and the temperature onset for the formation of polycrystalline aggregates. The results demonstrate that at 550 °C we obtain pure single-phase equiaxed nanopowders of LaCoO 3 with crystal size of 20 nm, free of amorphous carbon and without the presence of polycrystalline aggregates.

Microstructure and secondary phase segregation correlation in epitaxial/oriented ZnO films with unfavorable Cr dopant

Low solubility dopant-host systems are well suited to study secondary phase segregation-microstructure dependence. We discuss the effect of microstructure on secondary phase segregation in epitaxial/oriented ZnO thin films with Cr as an unfavorable dopant (Cr:ZnO). Since differences in thin film microstructure are a function of the substrate and its orientation, simultaneous chemical vapor depositions were carried out on single crystals of Si (100), c-axis oriented Al2O3 (c-ALO), and r-axis oriented Al2O3 (r-ALO) resulting in epitaxial film growth on r-ALO and c-axis oriented film growth on Si and c-ALO, with a difference in vertical grain boundary density. To enhance the analysis sensitivity to the microstructure difference, the thickness of Cr:ZnO films was maintained at ∼50 nm. High-resolution transmission electron microscopy (HRTEM) analysis indicates uniform stress distribution in Cr:ZnO grown on r-ALO. Surface sensitive x-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) techniques were utilized for analysis of the data. We observe that a higher grain boundary density and the presence of an amorphous layer at the interface for films grown on Si(100) single crystal led to interfacial Cr-based secondary phase segregation as opposed to lower grain boundary density and epitaxial films grown on c-ALO and r-ALO single crystals, respectively. We also discuss the effects of trace carbon solubility on the film microstructure/secondary phase segregation relationship.

High-resolution analytical electron microscopy of catalytically etched silicon nanowires

We report on the characterization of hexagonally ordered, vertically aligned silicon nanowires (SiNW) by means of analytical transmission electron microscopy. Combining colloidal lithography, plasma etching, and catalytic wet etching arrays of SiNW of a sub-50 nm diameter with an aspect ratio of up to 10 could be fabricated. Scanning transmission electron microscopy has been applied in order to investigate the morphology, the internal structure, and the composition of the catalytically etched SiNW. The analysis yielded a single-crystalline porous structure composed of crystalline silicon, amorphous silicon, and SiOx with x≤2.