Deflecting Dendrites by Introducing Compressive Stress in Li7La3Zr2O12 Using Ion Implantation.

Lithium dendrites belong to the key challenges of solid-state battery research. They are unavoidable due to the imperfect nature of surfaces containing defects of a critical size that can be filled by lithium until fracturing the solid electrolyte. The penetration of Li metal occurs along the propagating crack until a short circuit takes place. It is hypothesized that ion implantation can be used to introduce stress states into Li6.4La3Zr1.4Ta0.6O12 which enables an effective deflection and arrest of dendrites. The compositional and microstructural changes associated with the implantation of Ag-ions are studied via atom probe tomography, electron microscopy, and nano X-ray diffraction indicating that Ag-ions can be implanted up to 1 µm deep and amorphization takes place down to 650-700 nm, in good agreement with kinetic Monte Carlo simulations. Based on diffraction results pronounced stress states up to -700 MPa are generated in the near-surface region. Such a stress zone and the associated microstructural alterations exhibit the ability to not only deflect mechanically introduced cracks but also dendrites, as demonstrated by nano-indentation and galvanostatic cycling experiments with subsequent electron microscopy observations. These results demonstrate ion implantation as a viable technique to design "dendrite-free" solid-state electrolytes for high-power and energy-dense solid-state batteries.

Operando Spatial and Temporal Tracking of Axial Stresses and Interfaces in Solid-state Batteries.

Solid-state batteries have the potential to replace the current generation of liquid electrolyte batteries. However, the major limitation resulting from their solid-state architecture is the gradual loss of ionic conductivity due to the loss of physical contact between the individual battery components during charging/discharging. This is mainly due to mechanical stresses caused by volume changes in the cathode and anode during lithiation and delithiation. To date, limited research has been devoted to understanding the spatio-temporal distribution of stresses during battery operation. Here, operando scanning high-energy X-ray diffraction to quantify cross-sectional axial stresses with a spatial resolution of 10 µm is used. It is shown how a non-monotonous stress distribution evolves over time during the cycling of the solid-state battery. In addition, degradation of the solid-state electrolyte in the vicinity of the lithium anode is observed and tracked periodic changes in the unit cell volume in the cathode. The presented methodology of tracking the chemo-mechanically induced stresses and interface morphology in real time in correlation with other battery parameters is believed, can provide a valuable platform for the future optimization of solid-state batteries.

Probing the composition dependence of residual stress distribution in tungsten-titanium nanocrystalline thin films.

Nanocrystalline alloy thin films offer a variety of attractive properties, such as high hardness, strength and wear resistance. A disadvantage is the large residual stresses that result from their fabrication by deposition, and subsequent susceptibility to defects. Here, we use experimental and modelling methods to understand the impact of minority element concentration on residual stresses that emerge after deposition in a tungsten-titanium film with different titanium concentrations. We perform local residual stress measurements using micro-cantilever samples and employ machine learning for data extraction and stress prediction. The results are correlated with accompanying microstructure and elemental analysis as well as atomistic modelling. We discuss how titanium enrichment significantly affects the stress stored in the nanocrystalline thin film. These findings may be useful for designing stable nanocrystalline thin films.

Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering.

Application of low-cost carbon black from lignin highly depends on the materials properties, which might by determined by raw material and processing conditions. Four different technical lignins were subjected to thermostabilization followed by stepwise heat treatment up to a temperature of 2000 °C in order to obtain micro-sized carbon particles. The development of the pore structure, graphitization and inner surfaces were investigated by X-ray scattering complemented by scanning electron microscopy and FTIR spectroscopy. Lignosulfonate-based carbons exhibit a complex pore structure with nanopores and mesopores that evolve by heat treatment. Organosolv, kraft and soda lignin-based samples exhibit distinct pores growing steadily with heat treatment temperature. All carbons exhibit increasing pore size of about 0.5-2 nm and increasing inner surface, with a strong increase between 1200 °C and 1600 °C. The chemistry and bonding nature shifts from basic organic material towards pure graphite. The crystallite size was found to increase with the increasing degree of graphitization. Heat treatment of just 1600 °C might be sufficient for many applications, allowing to reduce production energy while maintaining materials properties.

Influence of Fiber Deviation on Strength of Thin Birch (Betula pendula Roth.) Veneers.

The currently pursued implementation of wood into novel high performance applications such as automotive parts require knowledge about the material behaviour including ultimate strength. Previous research has shown that fiber deviation seems to be the dominating factor influencing the strength of thin veneers. This study aims to further investigate and quantify the influence of fiber deviation in two dimension and different hierarchical levels on the tensile strength of thin birch veneers. The fiber deviation in- and out-of-plane as well as the micro fibril angle were assessed by means of wide-angle X-ray scattering. Tensile strength was determined in laboratory experiments. Results show a high variability for in-plane fiber deviation mainly constituted by knots and other growth influencing factors. Pearson correlations between strength and fiber deviation ranged from -0.594 up to -0.852. Best correlation (r = -0.852) was achieved for maximum in-plane fiber deviation directly followed by a combined angle of in- and out-of-plane fiber deviation (r = -0.846). Based on the results it was shown that fiber deviation in- and out-of-plane is the dominating factor influencing ultimate tensile strength of thin birch veneers. Further research in regard to non-destructive strength prediction is necessary.

Biomimetic hard and tough nanoceramic Ti-Al-N film with self-assembled six-level hierarchy.

Nature uses self-assembly of a fairly limited selection of components to build hard and tough protective tissues like nacre and enamel. The resulting hierarchical micro/nanostructures provide decisive toughening mechanisms while preserving strength. However, to mimic microstructural and mechanical characteristics of natural materials in application-relevant synthetic nanostructures has proven to be difficult. Here, we demonstrate a biomimetic synthesis strategy, based on chemical vapour deposition technology, employed to fabricate a protective high-temperature resistant nanostructured ceramic TiAlN thin film with six levels of hierarchy. By using just two variants of gaseous precursors and through bottom-up self-assembly, an irregularly arranged hard and tough multilayer stack was formed, consisting of hard sublayers with herringbone micrograins, separated by tough interlayers with spherical nanograins, respectively composed of lamellar nanostructures of alternating coherent/incoherent, hard/tough, single-/poly-crystalline platelets. Micro- and nanomechanical testing, performed in situ in scanning and transmission electron microscopes, manifests intrinsic toughening mechanisms mediated by five types of interfaces resulting in intergranular, transgranular and cleavage fracture modes with zigzag-like crack patterns at multiple length-scales. The hierarchical 2.7 µm thick film self-assembled during ∼15 minutes of deposition time shows hardness, fracture stress and toughness of ∼31 GPa, ∼7.9 GPa and ∼4.7 MPa m0.5, respectively, as well as phase/microstructural thermal stability up to ∼950/900 °C. The film's microstructural and mechanical characteristics represent a milestone in the production of protective and wear-resistant thin films.

Study of CuO Nanowire Growth on Different Copper Surfaces.

Cupric oxide (CuO) nanowires were produced by thermal oxidation of copper surfaces at temperatures up to 450 °C. Three different surfaces, namely a copper foil as well as evaporation deposited copper and an application relevant sputtered copper film on Si(100) substrates were characterized ex-situ before and after the experiment. The development of oxide layers and nanowires were monitored in-situ using grazing incidence small angle X-ray scattering. The number density of nanowires is highest for the sputtered surface and lowest for the surface prepared by evaporation deposition. This can be linked to different oxide grain sizes and copper grain boundary diffusions on the different surfaces. Small grains of the copper substrate and high surface roughness thereby lead to promoted growth of the nanowires.

Facile preparation of superhydrophobic wood surfaces via spraying of aqueous alkyl ketene dimer dispersions.

The prevention of excessive water uptake in wood in order to avert discoloration, swelling and decay is a major challenge for wood-based applications. We developed a facile surface treatment to protect wood from liquid water uptake that does not require harsh process conditions or toxic solvents. Water-based and surfactant-free dispersions of sub-micron alkyl ketene dimer wax particles were prepared and sprayed onto wood substrates. After the evaporation of water, the wax particles self-assembled into distinctive platelet structures. Depending on the specific conditions of application, water contact angles as high as 166° were measured on treated wood surfaces. The implementation of sub-micro structures clearly reduced surface gloss but transparency and color remained largely unaffected. The method is comparably cost-effective and scalable, overcoming dimensional limitations crucial for many applications of wood.

Electrically-Conductive Sub-Micron Carbon Particles from Lignin: Elucidation of Nanostructure and Use as Filler in Cellulose Nanopapers.

Carbon particles were produced from kraft lignin through carbonization of perfectly spherical, sub-micron beads obtained by aerosol flow. The structure of the resulting carbon particles was elucidated and compared to that derived from commercially available technical lignin powder, which is undefined in geometry. In addition to the smaller diameters of the lignin beads (<1 µm) compared to those of the lignin powder (100 µm), the former displayed a slightly higher structural order as revealed by X-ray diffraction and Raman spectroscopy. With regard to potential application in composite structures, the sub-micron carbon beads were clearly advantageous as a filler of cellulose nanopapers, which displayed better mechanical performance but with limited electrical conductivity. Compression sensing was achieved for this nanocomposite system.

Cross-sectional TEM study of subsurface damage in SPDT machining of germanium optics.

In addition to surface roughness and shape precision, the subsurface damage (SSD) generated by single point diamond turning (SPDT) of Ge and Si crystal optics is of increasing importance with decreasing wavelength from infrared through visible, UV, and x-ray. There are various components of SSD, e.g., microcracks, dislocations, strain, and a near-surface amorphous layer, and there are also several techniques to evaluate various components of SSD. Cross-sectional transmission electron microscopy (XTEM) is expensive and not often directly used in the optics laboratory. However, because of its very high sensitivity to SSD and down to atomic resolution, it is often used as an external service for developing SPDT technology and other surface processing techniques. It is shown in the paper that improper sample preparation can generate near-surface amorphization. Measures to avoid this artifact and a test of reliability of XTEM sample preparation are proposed.

Lignocellulose Nanofiber-Reinforced Polystyrene Produced from Composite Microspheres Obtained in Suspension Polymerization Shows Superior Mechanical Performance.

A facile approach to obtaining cellulose nanofiber-reinforced polystyrene with greatly improved mechanical performance compared to unreinforced polystyrene is presented. Cellulose nanofibers were obtained by mechanical fibrillation of partially delignified wood (MFLC) and compared to nanofibers obtained from bleached pulp. Residual hemicellulose and lignin imparted amphiphilic surface chemical character to MFLC, which enabled the stabilization of emulsions of styrene in water. Upon suspension polymerization of styrene from the emulsion, polystyrene microspheres coated in MFLC were obtained. When processed into polymer sheets by hot-pressing, improved bending strength and superior impact toughness was observed for the polystyrene-MFLC composite compared to the un-reinforced polystyrene.

In-situ Observation of Cross-Sectional Microstructural Changes and Stress Distributions in Fracturing TiN Thin Film during Nanoindentation.

Load-displacement curves measured during indentation experiments on thin films depend on non-homogeneous intrinsic film microstructure and residual stress gradients as well as on their changes during indenter penetration into the material. To date, microstructural changes and local stress concentrations resulting in plastic deformation and fracture were quantified exclusively using numerical models which suffer from poor knowledge of size dependent material properties and the unknown intrinsic gradients. Here, we report the first in-situ characterization of microstructural changes and multi-axial stress distributions in a wedge-indented 9 µm thick nanocrystalline TiN film volume performed using synchrotron cross-sectional X-ray nanodiffraction. During the indentation, needle-like TiN crystallites are tilted up to 15 degrees away from the indenter axis in the imprint area and strongly anisotropic diffraction peak broadening indicates strain variation within the X-ray nanoprobe caused by gradients of giant compressive stresses. The morphology of the multiaxial stress distributions with local concentrations up to -16.5 GPa correlate well with the observed fracture modes. The crack growth is influenced decisively by the film microstructure, especially by the micro- and nano-scopic interfaces. This novel experimental approach offers the capability to interpret indentation response and indenter imprint morphology of small graded nanostructured features.

Carbon Microparticles from Organosolv Lignin as Filler for Conducting Poly(Lactic Acid).

Carbon microparticles were produced from organosolv lignin at 2000 °C under argon atmosphere following oxidative thermostabilisation at 250 °C. Scanning electron microscopy, X-ray diffraction, small-angle X-ray scattering, and electro-conductivity measurements revealed that the obtained particles were electrically conductive and were composed of large graphitic domains. Poly(lactic acid) filled with various amounts of lignin-derived microparticles showed higher tensile stiffness increasing with particle load, whereas strength and extensibility decreased. Electric conductivity was measured at filler loads equal to and greater than 25% w/w.

Synergy of multi-scale toughening and protective mechanisms at hierarchical branch-stem interfaces.

Biological materials possess a variety of artful interfaces whose size and properties are adapted to their hierarchical levels and functional requirements. Bone, nacre, and wood exhibit an impressive fracture resistance based mainly on small crystallite size, interface organic adhesives and hierarchical microstructure. Currently, little is known about mechanical concepts in macroscopic biological interfaces like the branch-stem junction with estimated 10(14) instances on earth and sizes up to few meters. Here we demonstrate that the crack growth in the upper region of the branch-stem interface of conifer trees proceeds along a narrow predefined region of transversally loaded tracheids, denoted as sacrificial tissue, which fail upon critical bending moments on the branch. The specific arrangement of the tracheids allows disconnecting the overloaded branch from the stem in a controlled way by maintaining the stem integrity. The interface microstructure based on the sharply adjusted cell orientation and cell helical angle secures a zig-zag crack propagation path, mechanical interlock closing after the bending moment is removed, crack gap bridging and self-repairing by resin deposition. The multi-scale synergetic concepts allows for a controllable crack growth between stiff stem and flexible branch, as well as mechanical tree integrity, intact physiological functions and recovery after the cracking.

X-ray analysis of residual stress gradients in TiN coatings by a Laplace space approach and cross-sectional nanodiffraction: a critical comparison.

Novel scanning synchrotron cross-sectional nanobeam and conventional laboratory as well as synchrotron Laplace X-ray diffraction methods are used to characterize residual stresses in exemplary 11.5 µm-thick TiN coatings. Both real and Laplace space approaches reveal a homogeneous tensile stress state and a very pronounced compressive stress gradient in as-deposited and blasted coatings, respectively. The unique capabilities of the cross-sectional approach operating with a beam size of 100 nm in diameter allow the analysis of stress variation with sub-micrometre resolution at arbitrary depths and the correlation of the stress evolution with the local coating microstructure. Finally, advantages and disadvantages of both approaches are extensively discussed.

Cellulose nanofibrils as filler for adhesives: effect on specific fracture energy of solid wood-adhesive bonds.

Cellulose nanofibrils were prepared by mechanical fibrillation of never-dried beech pulp and bacterial cellulose. To facilitate the separation of individual fibrils, one part of the wood pulp was surface-carboxylated by a catalytic oxidation using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as a catalyst. After fibrillation by a high pressure homogenizer, the obtained aqueous fibril dispersions were directly mixed with different urea-formaldehyde-(UF)-adhesives. To investigate the effect of added cellulose filler on the fracture mechanical properties of wood adhesive bonds, double cantilever beam specimens were prepared from spruce wood. While the highest fracture energy values were observed for UF-bonds filled with untreated nanofibrils prepared from wood pulp, bonds filled with TEMPO-oxidized fibrils showed less satisfying performance. It is proposed that UF-adhesive bonds can be significantly toughened by the addition of only small amounts of cellulose nanofibrils. Thereby, the optimum filler content is largely depending on the adhesive and type of cellulose filler used.

Converse piezoelectric effect in cellulose I revealed by wide-angle X-ray diffraction.

The converse piezoelectric effect in cellulose I was studied by exposing thin pine wood slices to an electric field. Macroscopically, a strong extension of wood was observed in its transverse anatomical direction (grain angle 90 degrees), perpendicular to the direction of the electric field. The same effect, albeit to a lesser extent, was observed for specimens with a 45 degree grain angle, whereas no measurable dimensional change was observed for specimens with grain oriented parallel to the testing direction (0 degree grain angle). The measured extension in the transverse direction was proportional to the intensity of the applied electric field and amounted to 0.0278% on average at a field intensity of 1 MV m(-1), which results in a piezoelectric charge constant of 278 pm V(-1). At the nanoscale, changes in the cellulose crystallites due to the applied electric field were studied by means of wide-angle X-ray diffraction using the same specimens as in macroscopic experiments. Significant radial shifts of the scattering intensity peak attributed to the cellulose 200 crystallographic plane toward smaller scattering angles were observed, while the electric field was applied. These peak shifts were attributed to an increase in the spacing of the 200 crystallographic planes of cellulose I. At an electric field intensity of 1 MV m(-1), a crystallite strain epsilon(perpendicular 200) normal to the 200 reflection plane of 0.2% was estimated from Bragg's law.

Kinetics of nanoparticle reassembly mediated by UV-photolysis of surfactant.

Real-time reassembly of an ordered nanoparticle monolayer due to UV-photolysis of the surfactant shell of nanoparticles was observed. The technique of grazing-incidence small-angle X-ray scattering provided the possibility to track in situ the nanoparticle pair correlation function of the sample processed in a UV-ozone reactor. The analysis revealed a total shift of approximately 1 nm of the nanoparticle nearest-neighbor distance. The temporal evolution of the interparticle distance proved to be the first-order process governed by the UV-photolysis and described by a single-exponential decay function. The nanoparticles tend to agglomerate into a labyrinth-like structure with a typical length scale of some 30 nm.

Cellulose in never-dried gel oriented by an AC electric field.

Never-dried cellulose gel obtained by slow coagulation from LiCl/N,N-dimethylacetamide (DMAc) solution was exposed to an alternating current electric field. Making use of the birefringence of oriented cellulose and by means of wide-angle X-ray scattering, it was demonstrated that preferred orientation of cellulose molecules parallel to the electric field lines is induced in the cellulose gel. The preferred orientation remained unchanged for several days after storage in water and persisted after drying of the cellulose gel.

Actual versus apparent within cell wall variability of nanoindentation results from wood cell walls related to cellulose microfibril angle.

Hardness and elastic modulus of spruce wood cell walls parallel to their axial direction were investigated by means of nanoindentation. In the secondary cell wall layer S2 of individual earlywood and compression wood tracheids, a systematic pattern variability was found. Several factors potentially affecting nanoindentation results were investigated, i.e. specimen orientation related to the indenter tip, cutting direction during specimen preparation, tip geometry, specimen and fibre inclination, respectively, and finally micro fibril orientation. Mechanical property measurements were correlated with structural features measured by confocal Raman spectroscopy. It was demonstrated that very high variability in the measurement of micromechanical cell wall properties can be caused by unintentional small fibre misalignment by few degrees with regard to the indentation direction caused by sub-optimal specimen preparation.