Mechanism of WS2 Nanotube Formation Revealed by in Situ/ex Situ Imaging.

Multiwall WS2 nanotubes have been synthesized from W18O49 nanowhiskers in substantial amounts for more than a decade. The established growth model is based on the "surface-inward" mechanism, whereby the high-temperature reaction with H2S starts on the nanowhisker surface, and the oxide-to-sulfide conversion progresses inward until hollow-core multiwall WS2 nanotubes are obtained. In the present work, an upgraded in situ SEM µReactor with H2 and H2S sources has been conceived to study the growth mechanism in detail. A hitherto undescribed growth mechanism, named "receding oxide core", which complements the "surface-inward" model, is observed and kinetically evaluated. Initially, the nanowhisker is passivated by several WS2 layers via the surface-inward reaction. At this point, the diffusion of H2S through the already existing outer layers becomes exceedingly sluggish, and the surface-inward reaction is slowed down appreciably. Subsequently, the tungsten suboxide core is anisotropically volatilized within the core close to its tips. The oxide vapors within the core lead to its partial out-diffusion, partially forming a cavity that expands with reaction time. Additionally, the oxide vapors react with the internalized H2S gas, forming fresh WS2 layers in the cavity of the nascent nanotube. The rate of the receding oxide core mode increases with temperatures above 900 °C. The growth of nanotubes in the atmospheric pressure flow reactor is carried out as well, showing that the proposed growth model (receding oxide core) is also relevant under regular reaction parameters. The current study comprehensively explains the WS2 nanotube growth mechanism, combining the known model with contemporary insight.

W18O49 Nanowhiskers Decorating SiO2 Nanofibers: Lessons from In Situ SEM/TEM Growth to Large Scale Synthesis and Fundamental Structural Understanding.

Tungsten suboxide W18O49 nanowhiskers are a material of great interest due to their potential high-end applications in electronics, near-infrared light shielding, catalysis, and gas sensing. The present study introduces three main approaches for the fundamental understanding of W18O49 nanowhisker growth and structure. First, W18O49 nanowhiskers were grown from γ-WO3/a-SiO2 nanofibers in situ in a scanning electron microscope (SEM) utilizing a specially designed microreactor (µReactor). It was found that irradiation by the electron beam slows the growth kinetics of the W18O49 nanowhisker, markedly. Following this, an in situ TEM study led to some new fundamental understanding of the growth mode of the crystal shear planes in the W18O49 nanowhisker and the formation of a domain (bundle) structure. High-resolution scanning transmission electron microscopy analysis of a cross-sectioned W18O49 nanowhisker revealed the well-documented pentagonal Magnéli columns and hexagonal channel characteristics for this phase. Furthermore, a highly crystalline and oriented domain structure and previously unreported mixed structural arrangement of tungsten oxide polyhedrons were analyzed. The tungsten oxide phases found in the cross section of the W18O49 nanowhisker were analyzed by nanodiffraction and electron energy loss spectroscopy (EELS), which were discussed and compared in light of theoretical calculations based on the density functional theory method. Finally, the knowledge gained from the in situ SEM and TEM experiments was valorized in developing a multigram synthesis of W18O49/a-SiO2 urchin-like nanofibers in a flow reactor.

Real-Time Study of Surface-Guided Nanowire Growth by In Situ Scanning Electron Microscopy.

Surface-guided growth has proven to be an efficient approach for the production of nanowire arrays with controlled orientations and their large-scale integration into electronic and optoelectronic devices. Much has been learned about the different mechanisms of guided nanowire growth by epitaxy, graphoepitaxy, and artificial epitaxy. A model describing the kinetics of surface-guided nanowire growth has been recently reported. Yet, many aspects of the surface-guided growth process remain unclear due to a lack of its observation in real time. Here we observe how surface-guided nanowires grow in real time by in situ scanning electron microscopy (SEM). Movies of ZnSe surface-guided nanowires growing on periodically faceted substrates of annealed M-plane sapphire clearly show how the nanowires elongate along the substrate nanogrooves while pushing the catalytic Au nanodroplet forward at the tip of the nanowire. The movies reveal the timing between competing processes, such as planar vs nonplanar growth, catalyst-selective vapor-liquid-solid elongation vs nonselective vapor-solid thickening, and the effect of topographic discontinuities of the substrate on the growth direction, leading to the formation of kinks and loops. Contrary to some observations for nonplanar nanowire growth, planar nanowires are shown to elongate at a constant rate and not by jumps. A decrease in precursor concentration as it is consumed after long reaction time causes the nanowires to shrink back instead of growing, thus indicating that the process is reversible and takes place near equilibrium. This real-time study of surface-guided growth, enabled by in situ SEM, enables a better understanding of the formation of nanostructures on surfaces.

Surface Modification of Metallic Inserts for Enhancing Adhesion at the Metal-Polymer Interface.

A combination of mechanical and chemical treatments was utilized to modify the surface textures of copper and duralumin inserts in order to enhance the adhesion at the metal-polymer interface and provide an adhesive joint with a high loadbearing capacity. Pretreatment of the surfaces with sandblasting was followed by etching with various chemical mixtures. The resulting surface textures were evaluated with a scanning electron microscope (SEM) and an optical confocal microscope. Surface geometry parameters (Sa, Sz, and Sdr) were measured and their relationships to the adhesion joint strength were studied. It was found that the virgin and purely mechanically treated inserts resulted in joints with poor loadbearing capacity, while a hundredfold (duralumin) and ninetyfold (copper) increase in the force to break was observed for some combinations of mechanical and chemical treatments. It was determined that the critical factor is overcoming a certain surface roughness threshold with the mechanical pretreatment to maximize the potential of the mechanical/chemical approach for the particular combination of material and etchant.

Preparation of Textured Surfaces on Aluminum-Alloy Substrates.

The ways of producing porous-like textured surfaces with chemical etching on aluminum-alloy substrates were studied. The most appropriate etchants, their combination, temperature, and etching time period were explored. The influence of a specifically textured surface on adhesive joints' strength or superhydrophobic properties was evaluated. The samples were examined with scanning electron microscopy, profilometry, atomic force microscopy, goniometry, and tensile testing. It was found that, with the multistep etching process, the substrate can be effectively modified and textured to the same morphology, regardless of the initial surface roughness. By selecting proper etchants and their sequence one can prepare new types of highly adhesive or even superhydrophobic surfaces.

Silicon oxide nanowire growth mechanisms revealed by real-time electron microscopy.

Growth of one-dimensional materials is possible through numerous mechanisms that affect the nanowire structure and morphology. Here, we explain why a wide range of morphologies is observed when silicon oxide nanowires are grown on silicon substrates using liquid gallium catalyst droplets. We show that a gallium oxide overlayer is needed for nanowire nucleation at typical growth temperatures, and that it can decompose during growth and, hence, dramatically alter the nanowire morphology. Gallium oxide decomposition is attributed to etching caused by hydrogen that can be supplied by thermal dissociation of H2O (a common impurity). We show that H2O dissociation is catalyzed by silicon substrates at temperatures as low as 320 °C, identify the material supply pathways and processes that rate-limit nanowire growth under dry and wet atmospheres, and present a detailed growth model that explains contradictory results reported in prior studies. We also show that under wet atmospheres the Ga droplets can be mobile and promote nanowire growth as they traverse the silicon substrate.