Production of nanocellulose gels and films from invasive tree species.

Wood from invasive tree species Acacia dealbata and Ailanthus altissima was used to produce high value-added nanocellulose. Firstly, bleached pulps were produced from the wood of these tree species after kraft cooking. Afterwards, the resultant pulps were pre-treated by TEMPO-mediated oxidation (Acacia dealbata) or enzymatic hydrolysis (Ailanthus altissima) followed by high-pressure homogenization. Hydrogels were obtained and characterized for their main physical and chemical properties, including rheology measurements. After freeze-drying, the surface properties of the materials were evaluated by inverse gas chromatography. Results showed that nano/micro fibrils could be obtained from the wood of these invasive species. Rheometry studies showed that Acacia-TEMPO cellulose nanofibrils form strong gels with high yield stress point and viscosities (reaching ca. 100,000 Pa·s). Additionally, the surfaces of the obtained nanocelluloses showed a dispersive component of the surface energy near 40 mJ/m2 and a prevalence of the Lewis acidic character over the basic one, as typical for cellulose-based materials. Finally, films with good mechanical and optical properties could be obtained from the cellulose hydrogels. Acacia-TEMPO film (produced by filtration/hot pressing) showed a tensile strength of 79 MPa, Young's modulus of 7.9 GPa, and a transparency of 88%. The water vapor barrier, however, was modest (permeability of 4.9 × 10-6 g/(Pa·day·m)).

Manganese Migration in Li1-xMn2O4 Cathode Materials.

LiMn2O4 has been considered one of the most promising cathode materials for Li-ion batteries due to its thermal stability, abundance, environmental affinity, and the possibility to exchange Li-ions in three-dimensions. However, it still suffers from major problems, such as capacity fading and voltage decay, which has been associated to phase transformations and dissolution of transition metals. In this report, we use scanning transmission electron microscopy, coupled with differential phase contrast (DPC), to better understand the mechanisms behind the structural transformations occurring in LiMn2O4. We use the fact that DPC has the ability to observe simultaneously light and heavy elements, as well as measure projected electric fields and charge distribution at the atomic level. This approach allows us to monitor the migration of very low amounts of Mn to the Li atomic positions, at the surface and subsurface regions, which otherwise is very challenging to observe using other techniques such as HAADF and ABF. These observations not only provide a fundamental understanding of the structure of LiMn2O4 but also reveal DPC as a novel technique to determine local structural changes in materials consisting of heavy and light elements, as well as identify the location of light elements, monitor low concentrations of substitutional species and identify phase transformations.

Tuning rheology and aggregation behaviour of TEMPO-oxidised cellulose nanofibrils aqueous suspensions by addition of different acids.

The present work intends to study the variations in the rheological properties and aggregation behaviour of TEMPO-oxidised cellulose nanofibrils (CNF) aqueous suspensions, as a function of changes in concentration and systematic changes in the pH, by addition of acids with different anions. It was found that CNF suspensions form strong gels at mass fractions higher than 0.35 % and the gel point is ca. 0.18 %. On the other hand, aggregation is enhanced at acidic pH conditions due to lower charge repulsion among fibrils, leading to an increase of the suspension viscosity. However, distinct rheological behaviours were presented by CNF suspensions as different acids were applied. It was found that phosphate ions resulted in significant aggregation leading to formation of particles of large size and very strong gels, at pH 2.3; distinctly, the presence of acetate ions resulted in lower aggregation, lower particle size and weaker gels, at the same pH value.

Influence of initial chemical composition and characteristics of pulps on the production and properties of lignocellulosic nanofibers.

This work aimed to study the influence of the initial chemical composition (glucans, lignin, xylan, and mannans), intrinsic viscosity, and carboxylate groups of pulps on the production process and final properties of lignocellulosic nanofibers (LCNF). Pulps of pine sawdust, eucalyptus sawdust, and sugarcane bagasse subjected to conventional pulping and highly oxidized processes were the starting materials. The LCNF were obtained by TEMPO mediated oxidation and mechanical fibrillation with a colloidal grinder. The nanofibrillation degree, chemical charge content, rheology, laser profilometry, cristallinity and atomic force microscopy were used to characterize the LCNF. The carboxylate groups, hemicelluloses and lignin of the initial pulps were important factors that affected the production process of LCNF. The results revealed that intrinsic viscosity and carboxylate groups of the initial pulps affected LCNF production process, whereas lignin and hemicelluloses influenced the viscosity of LCNF aqueous suspensions, the roughness of LCNF films, and the carboxylate groups content of LCNF.

Automatic segmentation of inorganic nanoparticles in BF TEM micrographs.

Transmission electron microscopy (TEM) represents a unique and powerful modality for capturing spatial features of nanoparticles, such as size and shape. However, poor statistics arise as a key obstacle, due to the challenge in accurately and automatically segmenting nanoparticles in TEM micrographs. Towards remedying this deficit, we introduce an automatic particle picking device that is based on the concept of variance hybridized mean local thresholding. Validation of this new segmentation model is accomplished by applying a program written in Matlab to a database of 150 bright field TEM micrographs containing approximately 2,000 nanoparticles. We compare the results to global thresholding, local thresholding, and manual segmentation. It is found that this novel automatic particle picking device reduces false positives and false negatives significantly, while increasing the number of individual particles picked on regions of particle overlap.

Zinc nanostructures for oxygen scavenging.

In this work, oxidation of carbon supported Zn nanostructures was studied to elucidate their utilization as oxygen scavenging materials activated by the relative humidity in the environment. Moisture-activated nano-scavengers were produced on carbon substrates using magnetron sputtering attaining nano-islands (nanoparticles), randomly distributed on the carbon surface, with arbitrary crystallographic orientations. They possess a Zn-ZnO core-shell structure, caused by surface passivation, which provides them with a self-assembled protective layer that prevents complete oxidation of nanoparticles prior to utilization. The oxidation rate is independent of the nanoparticle size and orientation, for particles between 5 and 18 nm. The oxidation kinetics are not in complete agreement with the Cabrera and Mott theory. When exposed to a high relative humidity environment, an acceleration in the oxidation process is observed, dissolving the Zn nanoparticles and forming a layer on the carbon, which facilitates the consumption of the Zn to form ZnO. These results support the idea of its potential use in applications where high RH environments are required, such as food packaging.

Unique Combination of Surface Energy and Lewis Acid-Base Characteristics of Superhydrophobic Cellulose Fibers.

Cellulose fibers were first functionalized on their surface by silanization with trichloromethylsilane in an optimized gas-solid reaction, and the occurrence of the reaction was assessed using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. Then, the changes in the physicochemical surface properties of the material were thoroughly assessed using inverse gas chromatography (IGC) and X-ray photoelectron spectroscopy as surface specific tools. A very surprising combination of results was obtained: (i) the dispersive component of the surface energy was found to decrease from 42 to 14 mJ m-2 (at 40 °C), the latter figure representing one of the lowest values ever reported (by IGC) for cellulose-based materials, and (ii) both Lewis acidic and Lewis basic characters of the fiber surface, as measured by the injection into the IGC columns of 15 different vapor probes, significantly increased with silanization. Moreover, those remarkable changes in the surface properties of the material were obtained at a low degree of silanization (as shown by ATR-FTIR). The present results may have a great impact in what concerns the application of the described type of superhydrophobic cellulose fibers for the production of new biocomposites: an unusual enhanced compatibility both with low-surface energy polymeric matrices, such as polyolefins, as well as with other types of matrices through Lewis acid-base interactions, can be predicted.

Patterns of tick infestation and their Borrelia burgdorferi s.l. infection in wild birds in Portugal.

Wild birds may act as reservoirs for zoonotic pathogens and may be mechanical carriers of pathogen infected vector ticks through long distances during migration. The aim of this study was to assess tick infestation patterns in birds in Portugal and the prevalence of tick infection by Borrelia burgdorferi s.l. using PCR techniques. Seven tick species were collected from birds including Haemaphysalis punctata, Hyalomma spp., Ixodes acuminatus, Ixodes arboricola, Ixodes frontalis, Ixodes ricinus and Ixodes ventalloi. We found that I. frontalis and Hyalomma spp. were the most common ticks infesting birds of several species and that they were widespread in Portugal. Turdus merula was the bird species that presented the highest diversity of infesting ticks and had one of the highest infestation intensities. B. burgdorferi s.l. was detected in 7.3% (37/505) of Ixodidae ticks derived from birds. The most common genospecies was Borrelia turdi (6.9%), detected in ticks collected from Parus major, T. merula and Turdus philomelos, but Borrelia valaisiana (0.2%) and one Borrelia sp. (0.2%) similar to Borrelia bissettii (96% of similarity of the flaB gene in Blastn) were also detected. This study contributed to a better knowledge of the Ixodidae tick fauna parasitizing birds in Western Europe and to the assessment of the prevalence of B. burgdorferi s.l. associated with birds and their ticks.

Effect of surface carbon coating on sintering of silver nanoparticles: in situ TEM observations.

In this work, in situ transmission electron microscopy heating has been used to investigate the effects of a carbon capping layer on sintering of silver nanoparticles. For the first time, we make direct and real-time measurements of surface diffusivity of silver in nanoparticles coated with carbon. We observe that the carbon surface coatings may significantly inhibit sintering in silver nanoparticles.

Grain boundary character distribution of nanocrystalline Cu thin films using stereological analysis of transmission electron microscope orientation maps.

Stereological analysis has been coupled with transmission electron microscope (TEM) orientation mapping to investigate the grain boundary character distribution in nanocrystalline copper thin films. The use of the nanosized (<5 nm) beam in the TEM for collecting spot diffraction patterns renders an order of magnitude improvement in spatial resolution compared to the analysis of electron backscatter diffraction patterns in the scanning electron microscope. Electron beam precession is used to reduce dynamical effects and increase the reliability of orientation solutions. The misorientation distribution function shows a strong misorientation texture with a peak at 60°/[111], corresponding to the Σ3 misorientation. The grain boundary plane distribution shows {111} as the most frequently occurring plane, indicating a significant population of coherent twin boundaries. This study demonstrates the use of nanoscale orientation mapping in the TEM to quantify the five-parameter grain boundary distribution in nanocrystalline materials.

A genomic distance for assembly comparison based on compressed maximal exact matches.

Genome assemblies are typically compared with respect to their contiguity, coverage, and accuracy. We propose a genome-wide, alignment-free genomic distance based on compressed maximal exact matches and suggest adding it to the benchmark of commonly used assembly quality metrics. Maximal exact matches are perfect repeats, without gaps or misspellings, which cannot be further extended to either their left- or right-end side without loss of similarity. The genomic distance here proposed is based on the normalized compression distance, an information-theoretic measure of the relative compressibility of two sequences estimated using multiple finite-context models. This measure exposes similarities between the sequences, as well as, the nesting structure underlying the assembly of larger maximal exact matches from smaller ones. We use four human genome assemblies for illustration and discuss the impact of genome sequencing and assembly in the final content of maximal exact matches and the genomic distance here proposed.

One-Step Hydrothermal Synthesis of Comb-Like ZnO Nanostructures.

Zinc Oxide (ZnO) nano-superstructures (NSSs) have attracted intense research interests due to their large surface areas and unique properties. In this work, we report an original approach to synthesize ZnO NSSs in a one-step manner with a hydrothermal method. The crystalline structures and growth mechanism can be understood by surface energy calculations. The reaction kinetics was investigated for the control of the morphology of ZnO NSSs. The critical role of the morphology of Au catalysts in the synthesis of ZnO nanostructures has been demonstrated. Such ZnO NSSs can be fabricated on various rigid and flexible substrates for applications in electronics, solar cells and piezoelectric devices.

In situ TEM nanoindentation of nanoparticles.

The deformation behavior of nanoparticles continues to be an exciting area for materials research. Typically, nanoparticles show a conspicuous lack of dislocations, even after significant deformation. Therefore, it has been suggested that dislocations cannot exist or/do not play a role on the deformation of nanoparticles. In situ TEM nanoindentation is a critical tool for addressing this issue because it allows for the deformation to be monitored in real time. In this article, we discuss some of the experimental needs and challenges for performing in situ nanoindentation TEM experiments on nanoparticles. In addition, we show both diffraction contrast and phase contrast in situ TEM nanoindentation experiments on silver nanoparticles with diameters below 50nm. Evidence of the presence of dislocations was observed during deformation, but upon unloading dislocations disappeared.

Effect of downscaling nano-copper interconnects on the microstructure revealed by high resolution TEM-orientation-mapping.

In this work, a recently developed electron diffraction technique called diffraction scanning transmission electron microscopy (D-STEM) is coupled with precession electron microscopy to obtain quantitative local texture information in damascene copper interconnects (1.8 µm-70 nm in width) with a spatial resolution of less than 5 nm. Misorientation and trace analysis is performed to investigate the grain boundary distribution in these lines. The results reveal strong variations in texture and grain boundary distribution of the copper lines upon downscaling. Lines of width 1.8 µm exhibit a strong <111> normal texture and comprise large micron-size grains. Upon downscaling to 180 nm, a {111}<110> bi-axial texture has been observed. In contrast, narrower lines of widths 120 and 70 nm reveal sidewall growth of {111} grains and a dominant <110> normal texture. The microstructure in these lines comprises clusters of small grains separated by high angle boundaries in the vicinity of large grains. The fraction of coherent twin boundaries also reduces with decreasing line width.

D-stem: a parallel electron diffraction technique applied to nanomaterials.

An electron diffraction technique called D-STEM has been developed in a transmission electron microscopy/scanning transmission electron microscopy (TEM/STEM) instrument to obtain spot electron diffraction patterns from nanostructures, as small as ∼3 nm. The electron ray path achieved by configuring the pre- and postspecimen illumination lenses enables the formation of a 1-2 nm near-parallel probe, which is used to obtain bright-field/dark-field STEM images. Under these conditions, the beam can be controlled and accurately positioned on the STEM image, at the nanostructure of interest, while sharp spot diffraction patterns can be simultaneously recorded on the charge-coupled device camera. When integrated with softwares such as GatanTM STEM diffraction imaging and Automated Crystallography for TEM or DigistarTM, NanoMEGAS, the D-STEM technique is very powerful for obtaining automated orientation and phase maps based on diffraction information acquired on a pixel by pixel basis. The versatility of the D-STEM technique is demonstrated by applying this technique to nanoparticles, nanowires, and nano interconnect structures.

In situ TEM study of grain growth in nanocrystalline copper thin films.

Nanocrystalline metals demonstrate a range of fascinating properties, including high levels of mechanical strength. However, as these materials are exposed to high temperatures, it is critical to determine the grain size evolution, as this process can drastically change the mechanical properties. In this work, nanocrystalline sputtered Cu thin films with 43 +/- 2 nm grain size were produced by dc-magnetron sputtering. Specimens were subsequently annealed in situ in a transmission electron microscope at 100, 300 and 500 degrees C. Not only was grain growth more evident at 500 degrees C but also the fraction of twins found. An analysis of grain growth kinetics revealed a time exponent of 3 and activation energy of 35 kJ mol(-1). This value is explained by the high energy stored in the form of dislocation, grain boundaries and twin boundaries existing in nanocrystalline copper, as well as the high probability for atoms to move across grains in nanocrystalline materials.

Coalescence and sintering of Pt nanoparticles: in situ observation by aberration-corrected HAADF STEM.

An aberration-corrected JEOL 2200FS scanning-transmission electron microscope (STEM), equipped with a high-angle annular dark-field detector (HAADF), is used to monitor the coalescence and sintering of Pt nanoparticles with an average diameter of 2.8 nm. This in situ STEM capability is combined with an analysis methodology that together allows direct measurements of mass transport phenomena that are important in understanding how particle size influences coalescence and sintering at the nanoscale. To demonstrate the feasibility of this methodology, the surface diffusivity is determined from measurements obtained from STEM images acquired during the initial stages of sintering. The measured surface diffusivities are in reasonable agreement with measurements made on the surface of nanoparticles, using other techniques. In addition, the grain boundary mobility is determined from measurements made during the latter stages of sintering.

The influence of pulping and washing conditions on the properties of Eucalyptus grandis unbleached kraft pulps treated with chelants.

The influence of different addition points of a chelating agent and a counter-ion exchange on the properties of Eucalyptus grandis unbleached kraft pulps is studied. Seven pulps were considered: two laboratory kraft pulps with or without the inclusion of the chelant DTPMPA (diethylene triamine penta (methylene phosphonic acid)), a mill kraft pulp and four mill pulps after Ca(+2) or Na(+) counter-ion exchange followed, or not, by washing with DTPMPA addition. The laboratory pulps required lower beating energy than the industrial pulps for achieving 30 degrees SR, and the corresponding handsheets also showed better strength and optical properties, as well as a more homogeneous and smooth surface. The counter-ion exchange decreases the mechanical resistances and increases brightness. However, the effects of Ca(+2) are deeper than those of Na(+). DTPMPA added to pulping causes a decrease in calcium content whereas as a washing additive does not have a relevant impact on the mechanical and optical properties.

The effect of nitrogen on the formation of nanocrystalline copper thin films.

The current success of nanocrystalline materials is due to their unusual and promising properties compared to coarser grain size materials. However, maintaining the nanocrystalline character during processes or applications is not an easy task, due to the tendency towards grain growth exhibited by nanocrystalline materials. It is well known that the addition of solutes with a strong affinity for grain boundary segregation can act as pinning centers and inhibit grain growth, particularly during the manufacturing process. However, the ideal is to use these elements/compounds only during manufacturing, and after that these elements must disappear in order to attain the desirable properties. The aim of this study is to produce nanocrystalline Cu-based thin films through controlled addition of nitrogen to inhibit grain growth. A detailed chemical composition, structural and grain size analysis of these thin films was made by Electron Probe Microanalysis (EPMA), X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). The results indicate that introduction of nitrogen, even in small amounts, leads to a significant decrease in grain size, particularly if Cu3N is not yielded in the thin film during the deposition process.