Radial microfibril arrangements in wood cell walls.

MAIN CONCLUSION: TEM and AFM imaging reveal radial orientations and whorl-like arrangements of cellulose microfibrils near the S1/S2 interface. These are explained by wrinkling during lamellar cell growth. In the most widely accepted model of the ultrastructure of wood cell walls, the cellulose microfibrils are arranged in helical patterns on concentric layers. However, this model is contradicted by a number of transmission electron microscopy (TEM) studies which reveal a radial component to the microfibril orientations in the cell wall. The idea of a radial component of the microfibril directions is not widely accepted, since it cannot easily be explained within the current understanding of lamellar cell growth. To help clarify the microfibril arrangements in wood cell walls, we have investigated various wood cell wall sections using both transmission electron microscopy and atomic force microscopy, and using various imaging and specimen preparation methods. Our investigations confirm that the microfibrils have a radial component near the interface between the S1 and S2 cell wall layers, and also reveal a whorl-like microfibril arrangement at the S1/S2 interface. These whorl-like structures are consistent with cell wall wrinkling during growth, allowing the radial microfibril component to be reconciled with the established models for lamellar cell growth.

Polaronic Contributions to Friction in a Manganite Thin Film.

Despite the huge importance of friction in regulating movement in all natural and technological processes, the mechanisms underlying dissipation at a sliding contact are still a matter of debate. Attempts to explain the dependence of measured frictional losses at nanoscale contacts on the electronic degrees of freedom of the surrounding materials have so far been controversial. Here, it is proposed that friction can be explained by considering the damping of stick-slip pulses in a sliding contact. Based on friction force microscopy studies of La(1- x )Sr x MnO3 films at the ferromagnetic-metallic to a paramagnetic-polaronic conductor phase transition, it is confirmed that the sliding contact generates thermally-activated slip pulses in the nanoscale contact, and argued that these are damped by direct coupling into the phonon bath. Electron-phonon coupling leads to the formation of Jahn-Teller polarons and to a clear increase in friction in the high-temperature phase. There is neither evidence for direct electronic drag on the atomic force microscope tip nor any indication of contributions from electrostatic forces. This intuitive scenario, that friction is governed by the damping of surface vibrational excitations, provides a basis for reconciling controversies in literature studies as well as suggesting possible tactics for controlling friction.

The Structural Origins of Wood Cell Wall Toughness.

The remarkable mechanical stability of wood is primarily attributed to the hierarchical fibrous arrangement of the polymeric components. While the mechanisms by which fibrous cell structure and cellulose microfibril arrangements lend stiffness and strength to wood have been intensively studied, the structural origins of the relatively high splitting fracture toughness remain unclear. This study relates cellulose microfibril arrangements to splitting fracture toughness in pine wood cell walls using in situ electron microscopy and reveals a previously unknown toughening mechanism: the specific arrangement of cellulose microfibrils in the cell wall deflects cracks from the S2 layer to the S1/S2 interface, and, once there, causes the crack to be repetitively arrested and shunted along the interface in a zig-zag path. It is suggested that this natural adaptation of wood to achieve tough interfaces and then deflect and trap cracks at them can be generalized to provide design guidelines to improve toughness of high-performance and renewable engineering materials.

Magnetic Field-Assisted Chemical Vapor Deposition of Iron Oxide Thin Films: Influence of Field-Matter Interactions on Phase Composition and Morphology.

Magnetic field-assisted CVD offers a direct pathway to manipulate the evolution of microstructure, phase composition, and magnetic properties of the as-prepared film. We report on the role of applied magnetic fields (0.5 T) during a cold-wall CVD deposition of iron oxide from [FeIII(OtBu)3]2 leading to higher crystallinity, larger particulates, and better out-of-plane magnetic anisotropy, if compared with zero-field depositions. Whereas selective formation of homogeneous magnetite films was observed for the field-assisted process, coexistence of hematite and amorphous iron(III) oxide was confirmed under zero-field conditions. Comparison of the coercive field (11 vs 60 mT) indicated lower defect concentration for the field-assisted process with nearly superparamagnetic behavior. X-ray photoemission electron microscopy (X-PEEM) in absorption mode at the O-K and Fe-L3,2 edges confirmed the selective formation of magnetite (field-assisted) and hematite (zero-field) with coexisting amorphous phases, respectively, emphasizing the importance of field-matter interactions in the phase-selective synthesis of magnetic thin films.

Anisotropy control in magnetic nanostructures through field-assisted chemical vapor deposition.

Chemical vapor deposition of iron pentacarbonyl (Fe(CO)5) in an external magnetic field (B = 1.00 T) was found to significantly affect the microstructure and anisotropy of as-deposited iron crystallites that could be transformed into anisotropic hematite (α-Fe2O3) nanorods by aerobic oxidation. The deterministic influence of external magnetic fields on CVD deposits was found to be substrate-independent as demonstrated by the growth of anisotropic α-Fe columns on FTO (F:SnO2) and Si (100), whereas the films deposited in the absence of the magnetic field were constituted by isotropic grains. TEM images revealed gradual increase in average crystallite size in correlation to the increasing field strength and orientation, which indicates the potential of magnetic field-assisted chemical vapor deposition (mfCVD) in controlling the texture of the CVD grown thin films. Given the facet-dependent activity of hematite in forming surface-oxygenated intermediates, exposure of crystalline facets and planes with high atomic density and electron mobilities is crucial for oxygen evolution reactions. The field-induced anisotropy in iron nanocolumns acting as templates for growing textured hematite pillars resulted in two-fold higher photoelectrochemical efficiency for hematite films grown under external magnetic fields (J = 0.050 mA cm-2), when compared to films grown in zero field (J = 0.027 mA cm-2). The dark current measurements indicated faster surface kinetics as the origin of the increased catalytic activity.

Efficient, Self-Terminating Isolation of Cellulose Nanocrystals through Periodate Oxidation in Pickering Emulsions.

Many efforts have been made to isolate native nanocrystals from raw materials in the last two decades, such as cellulose nanocrystals (CNCs), but existing methods still suffer from low yields, complicated synthesis processes, and nonuniform sizes of obtained CNCs. This study concerns a facile, self-terminating, and efficient method for the formation of uniform CNCs in high yields during the periodate oxidation process within Pickering emulsions. A biphasic system containing hexane with dissolved hexylamine and an aqueous solution of sodium periodate (NaIO4 ) was used as the reaction medium. Regulated by hexylamine, owing to its limited solubility in water, the pH value of the aqueous phase was enhanced to around 9.8, leading to the precipitation of sodium orthoperiodate (Na2 H3 IO6 ) nanoplates and thus the formation of the initial Pickering emulsions. During the gradual formation of cellulose nanofibers and then CNCs, CNCs were attracted to stabilize the interface of the Pickering emulsions, which prevented further decomposition of CNCs by the oxidizing agent in aqueous suspensions. Thus, this isolation strategy secured the efficient separation of CNCs based on their own particular amphiphilic properties and achieved a high yield of up to 56 wt %.

Thermoreversible Self-Assembly of Perfluorinated Core-Coronas Cellulose-Nanoparticles in Dry State.

Self-assembly of nanoparticles (NPs) forming unique structures has been investigated extensively over the past few years. However, many self-assembled structures by NPs are irreversible, because they are generally constructed using their suspensions. It is still challenging for NPs to reversibly self-assemble in dry state, let alone of polymeric NPs with general sizes of hundreds of nm. Herein, this study reports a new reversible self-assembly phenomenon of NPs in dry state, forming thermoreversible strip-like supermolecular structures. These novel NPs of around 150 nm are perfluorinated surface-undecenoated cellulose nanoparticles (FSU-CNPs) with a core-coronas structure. The thermoreversible self-assembled structure is formed after drying in the air at the interface between FSU-CNP films and Teflon substrates. Remarkably, the formation and dissociation of this assembled structure are accompanied by a reversible conversion of the surface hydrophobicity, film transparency, and anisotropic properties. These findings show novel feasibility of reversible self-assembly of NPs in dry state, and thereby expand our knowledge of self-assembly phenomenon.

Characterization of Nanoporous Materials with Atom Probe Tomography.

A method to characterize open-cell nanoporous materials with atom probe tomography (APT) has been developed. For this, open-cell nanoporous gold with pore diameters of around 50 nm was used as a model system, and filled by electron beam-induced deposition (EBID) to obtain a compact material. Two different EBID precursors were successfully tested-dicobalt octacarbonyl [Co2(CO)8] and diiron nonacarbonyl [Fe2(CO)9]. Penetration and filling depth are sufficient for focused ion beam-based APT sample preparation. With this approach, stable APT analysis of the nanoporous material can be performed. Reconstruction reveals the composition of the deposited precursor and the nanoporous material, as well as chemical information of the interfaces between them. Thus, it is shown that, using an appropriate EBID process, local chemical information in three dimensions with sub-nanometer resolution can be obtained from nanoporous materials using APT.

Room temperature homogeneous ductility of micrometer-sized metallic glass.

Homogeneous ductile flow of metallic glasses is observed at the micrometer scale. It is shown that this unusual deformation mode of an otherwise brittle material depends on both specimen size and applied loading rate. The results are explained by intrinsic length-scale effects of nanometer-sized defects, and provide a rationale for the long term debated brittle-to-ductile transition of amorphous metals.

Ultrahigh strength single crystalline nanowhiskers grown by physical vapor deposition.

The strength of metal crystals is reduced below the theoretical value by the presence of dislocations or by flaws that allow easy nucleation of dislocations. A straightforward method to minimize the number of defects and flaws and to presumably increase its strength is to increase the crystal quality or to reduce the crystal size. Here, we describe the successful fabrication of high aspect ratio nanowhiskers from a variety of face-centered cubic metals using a high temperature molecular beam epitaxy method. The presence of atomically smooth, faceted surfaces and absence of dislocations is confirmed using transmission electron microscopy investigations. Tensile tests performed in situ in a focused-ion beam scanning electron microscope on Cu nanowhiskers reveal strengths close to the theoretical upper limit and confirm that the properties of nanomaterials can be engineered by controlling defect and flaw densities.

Time-resolved Laue diffraction of deforming micropillars.

We demonstrate real-time resolved white beam Laue diffraction during compression of micron-sized focused ion beam milled single crystals Au pillars, revealing the dynamical correlation between microstructure and plasticity. The evolution of the Laue patterns of the Au pillars demonstrates the occurrence of crystal rotation and strengthening is explained by plasticity starting on a slip system that is geometrically not predicted but selected because of the character of the preexisting strain gradient.

Size effects on the mechanical behavior of nanoporous Au.

Recent nanomechanical tests on submicron metal columns and wires have revealed a dramatic increase in yield strength with decreasing sample size. Here, we demonstrate that nanoporous metal foams can be envisioned as a three-dimensional network of ultrahigh-strength nanowires, thus bringing together two seemingly conflicting properties: high strength and high porosity. Specifically, we characterized the size-dependent mechanical properties of nanoporous gold using a combination of nanoindentation, column microcompression, and molecular dynamics simulations. We find that nanoporous gold can be as strong as bulk Au, despite being a highly porous material, and that the ligaments in nanoporous gold approach the theoretical yield strength of Au.

Analysis of local strain in aluminum interconnects by convergent beam electron diffraction.

Energy filtered convergent beam electron diffraction was used to investigate localized strain in aluminum interconnects. By analyzing the position of higher order Laue zone lines, it is possible to measure the three-dimensional lattice strain with high accuracy (approximately 10(-4)) and high spatial resolution (10 to 100 nm). In the present article, important details of the strain analysis procedure are outlined. Subsequently, results of measurements of the local variation of thermal strains in narrow, free-standing interconnects are presented. The strain development in single grains during thermal cycling between -170 degrees C and + 100 degrees C was measured in situ and local stress variations along the interconnect were investigated. The interconnects show reversible elastic behavior over the whole temperature range, leading to large stresses at low temperatures. The strain state varies locally within single grains, as well as from grain to grain, by as much as 50% in both types of samples. By comparing the experimental findings with elastic finite element modeling, a detailed understanding of the triaxial strain state could be achieved.