Nanometer-sized Structures Research Articles

Formation and strengthening mechanism of high entropy nugget for aluminum/steel resistance rivet welding

Resistance rivet welding (RRW) was a promising joining process for aluminum (Al) alloy and steel. The high entropy mixed nugget (HEMN) with the composition of Al0.8CoCrFe1.6Ni was obtained by introducing a high entropy alloy (HEA) rivet in RRW process. The high entropy played a significant role in facilitating the formation of solid solution. The HEMN microstructure exhibited a nanometer-sized weave-like structure caused by spinodal decomposition, comprising both BCC and B2 phases. The average hardness of the HEMN exceeded that of the Al/Steel mixed nugget, resulting in higher lap-shear strength and ductility. The analysis of strengthening mechanism demonstrated that the lattice misfit and order strengthening were the primary contributors. This study provided a novel strategy for joining dissimilar metal materials.

Benchmarking of X-Ray Fluorescence Microscopy with Ion Beam Implanted Samples Showing Detection Sensitivity of Hundreds of Atoms.

Single impurities in insulators are now often used for quantum sensors and single photon sources, while nanoscale semiconductor doping features are being constructed for electrical contacts in quantum technology devices, implying that new methods for sensitive, non-destructive imaging of single- or few-atom structures are needed. X-ray fluorescence (XRF) can provide nanoscale imaging with chemical specificity, and features comprising as few as 100000 atoms have been detected without any need for specialized or destructive sample preparation. Presently, the ultimate limits of sensitivity of XRF are unknown - here, gallium dopants in silicon are investigated using a high brilliance, synchrotron source collimated to a small spot. It is demonstrated that with a single-pixel integration time of 1 s, the sensitivity is sufficient to identify a single isolated feature of only 3000Ga impurities (a mass of just 350 zg). With increased integration (25 s), 650 impurities can be detected. The results are quantified using a calibration sample consisting of precisely controlled numbers of implanted atoms in nanometer-sized structures. The results show that such features can now be mapped quantitatively when calibration samples are used, and suggest that, in the near future, planned upgrades to XRF facilities might achieve single-atom sensitivity.

Cost-effective superhydrophobic ZnO films with adjustable wetting behaviors deposited via solution precursor plasma spray process

In this work, ZnO films featuring hierarchical micron−/nanometer-sized structures were deposited for adjusting wettability by a simple solution precursor plasma spray (SPPS) process using cost-effective zinc acetate solution. The effects of solution flow rate on the surface microstructures, surface roughness, crystalline orientation, and wetting behaviors of the films were investigated comprehensively. The results showed that high solution flow rate facilitated the formation of apparent hierarchical surface structures featuring more uniformly-distributed micron-sized protrusions and higher surface roughness. The increase of solution flow rate also promoted the crystalline growth along the non-polar (100) plane. With the solution flow rate increasing from 10 ml/min to 40 ml/min, the synergy of the surface structures and crystalline growth orientation resulted in a sharp decrease of the surface energy of the films from ~74.4 mJ/m2 to ~12.6 mJ/m2 and a dramatic elevation of water contact angles from ~130° to ~155°. The wetting states of different films were elucidated by correlating the wetting behaviors with the surface structures. The SPPS-deposited ZnO films showed high adhesion to water droplets, similar to the wetting behaviors of the petal effect, which could be used as a “mechanical hand” for non-loss microdroplet transfer. The work shows that SPPS represents a promising method to deposit cost-effective superhydrophobic films with adjustable wetting behaviors.

Effect of Nitrogen Ion Diffusion Jumps in Nanometer-Sized Si3N4 Memristors Investigated by Low-Frequency Noise Spectroscopy

The elementary jumps in the electron current through conducting filaments of two nanometer-sized virtual memristor structures consisting of a contact of a conductive atomic force microscope probe to the Si3N4 layer with the thickness of 6[Formula: see text]nm deposited onto the [Formula: see text]-Si(001) conductive substrates are investigated. These structures are: (S1) the Si3N4/Si film; (S2) the Si3N4/SiO2/Si stack, a similar structure with 2[Formula: see text]nm SiO2 sublayer between the film and the substrate. Usually, such investigations are performed by the analysis of the waveform of this current with the aim of extracting the random telegraph noise (RTN). Here, we develop a new indirect method, which is based on the measurement of the spectrum of the low-frequency flicker noise in the current without extracting the RTN. We propose that the flicker noise is caused by the motion (drift/diffusion) of nitrogen ions via vacancies within and around the filament. The number of these ions is estimated by taking into account the geometrical parameters of the filament. This allows us to estimate the root mean square magnitude [Formula: see text] of the current jumps, which are caused by random jumps of nitrogen ions, and the number M of these ions. This is fundamental for understanding the elementary mechanisms of the electron current flowing through the filament and the resistive switching in memristor devices.

Effects of Fe2O3-[BOx] reaction on sodium borosilicate glass structure doping with nano to macro sized α-Fe2O3 particles

Fe3+ is readily reacted with structural units to modify various properties of the borosilicate glasses and glass ceramics. However, there exists some controversies on Fe2O3 containing borosilicate glasses: (1) whether the Fe2O3 turned into the nanometer-sized polycrystalline structure or reacted with the glass matrix to form a new substance and (2) whether the role of Fe2O3 was depended on its concentration in the network of glass. Theoretical extinction spectra of α-Fe2O3 particles ranging from 1 to 180 nm in borosilicate glass align with UV–vis absorption spectra. Based on the Na2O-B2O3-Fe2O3 phase diagram, xFe2O3·(100-x) [41.6B2O3–20.7Na2O-19.2CaO-9.7Al2O3–7.0SiO2–0.6ZnO] (x=1.20∼1.95 mol%) were prepared for this study, analyzing from exterior characteristics to interior structure. Molecular vibrational spectroscopy and component structure measurement were applied to study the effect of doping α-Fe2O3 powders (particle sizes of 30 nm, 1 μm, 75 μm) on the sodium borosilicate glasses. Combination of experimental characterization and numerical simulation were also utilized to investigate the effects of iron oxide particle size on the color of dispersion systems. We discovered that (i) doping with either nanometer-sized or micron-sized particles of α-Fe2O3 can result in both the substitution for B3+ in tetra-coordination [BO4] and the bonding with [BO3] units within the amorphous network of sodium borosilicate glasses; (ii) Even at lower concentrations, α-Fe2O3 can still act as a network intermediate, combining both its former role and modifying properties. Based on these outcomes, for the reactive process, we formulated a constitutive model which offers valuable insights into understanding the behavior of iron oxide in sodium borosilicate glass. These findings are crucial for comprehending the processes involved in matrix preparation and are pivotal for progressing to the subsequent stage where designing and fabricating nanocomposite materials based on these matrices with spatial separation.

Recycling of hazardous jarosite residues based on hydrothermal crystal transformation

Jarosite [MeFe3(SO4)2(OH)6] is a typical non-ferrous smelting slag produced in the process of iron removal from hydrometallurgical solution, which contains a large number of valuable and toxic metal elements. Treating the complex and hazardous jarosite residue in an economically and environmentally sound way has always been an urgent problem. A novel one-step hydrothermal treatment method was proposed in this paper for recycling of jarosite residues. It can be seen from the XRD and TEM results that jarosite residues could be completely transformed into hematite crystal particles under hydrothermal conditions at temperature above 220℃. Meanwhile, other valuable metal components (such as nickel sulfate hexahydrate) entrained in the residue will be dissolved in the aqueous solution, which can be reused in the hydrometallurgical process. Through phase composition analysis of the hydrothermal process, it is concluded that jarosite was firstly pyrolyzed to generate Fe3+. The obtained Fe3+ was then hydrolyzed to Fe (OH)3, which was transformed into Fe2O3 through dehydration condensation and directional arrangement. Further roasting the hematite particles, the obtained product contained 62.57 % of Fe, but only 0.21 % of S and 0.04 % of As, which meets the requirements of raw materials for iron making. In addition, compared with the current international standard ISO 1248:2006 (E), the obtained hematite particles with nanometer size and single crystal structure can be used as iron oxide red pigment. Overall, the one-step hydrothermal treatment of jarosite residues followed by reduction roasting not only realizes the economic recycling of the metal resources, but also solves the stacking problem of those hazardous residues.

Isolation and Characteristics of Extracellular Vesicles Produced by Probiotics: Yeast Saccharomyces boulardii CNCM I-745 and Bacterium Streptococcus salivarius K12

Numerous probiotic microorganisms have repeatedly been shown to produce nanometer-sized structures named extracellular vesicles (EVs). Recently, it has been suggested that similarly to whole microbial cells, EVs produced by probiotics may also demonstrate health benefits to the host, while their application does not involve the risk of infection caused by live microorganisms. In this work, we isolated EVs from two probiotic species originating from different taxonomic domains — yeast Saccharomyces boulardii CNCM I-745 and bacterium Streptococcus salivarius K12. The diameters of S. boulardii EVs were about 142 nm and for S. salivarius EVs about 123 nm. For S. boulardii EVs, 1641 proteins and for S. salivarius EVs, 466 proteins were identified with a liquid chromatography-coupled tandem mass spectrometry and then functionally classified. In both microbial species, metabolic proteins significantly contributed to the cargo of EVs comprising 25% and 26% of all identified vesicular proteins for fungi and bacteria, respectively. Moreover, enzymes associated with cell wall rearrangement, including enzymatically active glucanases, were also identified in EVs. Furthermore, probiotic EVs were shown to influence host cells and stimulate the production of IL-1β and IL-8 by the human monocytic cell line THP-1, and, at the same time, did not cause any remarkable reduction in the survival rate of Galleria mellonella larvae in this invertebrate model commonly used to evaluate microbial EV toxicity. These observations suggest that the EVs produced by the investigated probiotic microorganisms may be promising structures for future use in pro-health applications.

Recent Developments of Femtosecond Laser Direct Writing for Meta-Optics.

Micro-optics based on the artificial adjustment of physical dimensions, such as the phase, polarization, and wavelength of light, constitute the basis of contemporary information optoelectronic technology. As the main means of optical integration, it has become one of the important ways to break through the future bottleneck of microelectronic technology. Geometric phase optical components can precisely control the polarization, phase, amplitude and other properties of the light field at the sub-wavelength scale by periodically arranging nanometer-sized unit structures. It has received extensive attention in the fields of holographic imaging and polarization optics. This paper reviews the physical mechanism of micro-nano structure modification, research progress of femtosecond laser direct-writing photoresist, femtosecond laser ablation of metal thin films, femtosecond laser-induced nanograting, and other methods for preparing polarization converters and geometric phase optics. The challenges of fabricating ultrafast optical devices using femtosecond laser technology are discussed.

Concise Synthesis of Molecular Hyperboloids by Oligomeric Macrocyclization of Octagonal Molecules.

Molecular hyperboloids were designed and synthesized. The synthesis was achieved by development of oligomeric macrocyclization of an octagonal molecule with a saddle shape. The saddle-shaped molecule, that is, [8]cyclo-meta-phenylene ([8]CMP), was decorated with two linkers for the oligomeric macrocyclization and was synthetically assembled by Ni-mediated Yamamoto coupling. Three congeners of the molecular hyperboloids (2mer-4mer) were obtained, and 2mer and 3mer were subjected to X-ray crystallographic analysis. Crystal structures revealed nanometer-sized hyperboloidal structures with 96π and 144π electrons, which also possessed nanopores on the curved molecular structures. Structures of [8]CMP cores of the molecular hyperboloids were compared with those of saddle-shaped phenine [8]circulene with a negative Gauss curvature to confirm their structural resemblance, which suggests further explorations of expanded networks of molecular hyperboloids.

Structural and optical properties of gold nanosponges revealed via 3D nano-reconstruction and phase-field models

Nanosponges are subject of intensive research due to their unique morphology, which leads among other effects to electrodynamic field localization generating a strongly nonlinear optical response at hot spots and thus enable a variety of applications. Accurate predictions of physical properties require detailed knowledge of the sponges’ chaotic nanometer-sized structure, posing a metrological challenge. A major goal is to obtain computer models with equivalent structural and optical properties. Here, to understand the sponges’ morphology, we present a procedure for their accurate 3D reconstruction using focused ion beam tomography. Additionally, we introduce a simulation method to create nanoporous sponge models with adjustable geometric properties. It is shown that if certain morphological parameters are similar for computer-generated and experimental sponges, their optical response, including magnitudes and hot spot locations, are also similar. Finally, we analyze the anisotropy of experimental sponges and present an easy-to-use method to reproduce arbitrary anisotropies in computer-generated sponges.

Interfacial Shear Strength of Single-Walled Carbon Nanotubes-Cement Composites from Molecular Dynamics and Finite Element Studies

Carbon nanotubes (CNTs) are nanometer-sized structures that can be used to reinforce cement matrices. The extent to which the mechanical properties are improved depends on the interfacial characteristics of the resulting materials, that is, on the interactions established between the CNTs and the cement. The experimental characterization of these interfaces is still impeded by technical limitations. The use of simulation methods has a great potential to give information about systems lacking experimental information. In this work, molecular dynamics (MD) and molecular mechanics (MM) were used in conjunction with finite element simulations to study the interfacial shear strength (ISS) of a structure formed by a pristine single-walled CNT (SWCNT) inserted in a tobermorite crystal. The results show that, for a constant SWCNT length, ISS values increase when the SWCNT radius increases, while for a constant SWCNT radius, shorter lengths enhance ISS values.

Origin of spin-glass-like magnetic anomaly in the superconducting and multiferroic spin ladder BaFe2Se3

The spin ladder system ${\mathrm{BaFe}}_{2}{\mathrm{Se}}_{3}$ presents puzzling magnetic behaviors, such as a spin-glass-like phase below $\ensuremath{\sim}50$ K. In this paper, an exchange bias effect with a large vertical shift in the field-cooled hysteresis loop is observed below 50 K. We also evidence the existence of uncompensated spins by susceptibility, magnetic remanence, and hysteresis loop measurements. The thermoremanent and isothermoremanent magnetization curves evidence a two-dimensional diluted antiferromagnet (DAFF) nature. Moreover, a nanometer-sized layered structure is observed by scanning electron microscope (SEM) and confirmed by scanning transmission electron microscope (STEM) coupled with electron energy loss spectroscopy (EELS). The discovery of exchange bias in antiferromagnetic ${\mathrm{BaFe}}_{2}{\mathrm{Se}}_{3}$ crystals adds a new dimension to the research of its superconducting and multiferroic properties.

Production of Cellulose and Chitin Nanofibers Based Masks for Protecting Against Corona Virus: A Review

The corona virus or SARS-CoV2 is a pathogenic virus that has become a pandemic and a threat in almost all countries in the world. SARS-CoV2 belongs to the Coronaviridae family with particle sizes varying around 60 nm - 140 nm. Various regulations and prevention have been designed to reduce the impact of Covid-19 by SARS-CoV2. Several technologies and studies have been developed to form nanofiber woven membranes. Cellulose nanofibers and chitin/chitosan nanofibers have been studied and are known to have nanometer-sized structures smaller than SARS-CoV2. Chitin/chitosan has been investigated to have antiviral properties, especially corona virus. Cellulose nanofibers, and chitin/chitosan nanofibers has the potential to be developed for Covid-19 virus nanofiltration masks. Various active agents (nanosilver, nanogold, CuO, etc.) have been known to have antiviral and/or antibacterial properties so that they can be used as nanofillers to enhance the performance and effectiveness of nanofibers based masks against SARS-CoV2.

Cryo ion polishing and high-resolution electron microscopy on a layered PEM composite of an automotive fuel cell

Abstract Gas and ion diffusivity within the membrane electrode assembly (MEA) are of central importance for the functioning of a proton exchange membrane (PEM) fuel cell. These properties are, among other things, directly impacted by the microstructure of the layering and the morphology of the individual layers. Different types of preparation were used to prepare the inner layer composite of the MEA/PEM of a fuel cell. The preparation quality provided for high resolution electron microscopy and the microstructure quantification were compared. The conventional mechanical preparation is compared to planar ion polishing, and cryo ion polishing at -80 °C. Advantages and disadvantages of the methods are discussed by way of examples related to the microstructure such as porosity, elemental distribution, and the measurement of the layer thickness. It is shown that cryo ion polishing facilitates a largely artifact-free preparation of the highly thermo-sensitive, partially highly porous layered PTFE composites, and the porous catalyst layers. Thus, not only easily ascertainable layer thicknesses but also qualitative features and important quantitative microstructural parameters, such as nanometer-sized pore structures and the porosity of the various composite layers can be revealed.

Co-Assembly of Diblock Copolymers and Molecular Bottlebrushes

Co-assembly of multicomponent polymers could promote the evolution of polymer assemblies into high-order nanostructures. The topological architecture of polymers is an important factor to affect their self-assembly behavior; however, the effect of topological architecture on the co-assembly behavior is still not clear. Herein, the aqueous co-assembly of poly(ethylene oxide)-block-polystyrene (PEG-b-PS) block copolymers (BCPs) and molecular bottlebrushes (MBBs) with polystyrene (PS) as side chains was conducted to investigate the effect of topological architecture on the co-assembly behavior. First, well-defined PEG-b-PS BCPs with varying degrees of polymerization (DP) of PEG and PS, and PS MBBs with different lengths (DP) of backbone were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP), respectively. By varying the DP of PS segments in BCPs and backbone length of MBBs as well as the mass ratio of BCPs and MBBs, various nanostructures ranging from spherical micelles to vesicles and large-compound vesicles (LCVs) were obtained. It was found that the insertion of the PS segment of block copolymers into the side chains of PS MBBs to stabilize MBBs in selective solvents is the key factor for the formation of stable nanometer-sized structures.

Electrically poled vapor-deposited organic glasses for integrated electro-optics.

We introduce electrically poled small molecule assemblies that can serve as the active electro-optic material in nano-scale guided-wave circuits such as those of the silicon photonics platform. These monolithic organic materials can be vacuum-deposited to homogeneously fill nanometer-size integrated-optics structures, and electrically poled at higher temperatures to impart an orientational non-centrosymmetric order that remains stable at room temperature. An initial demonstration using the DDMEBT molecule and corona poling delivered a material with the required high optical quality, an effective glass transition temperature of the order of ∼80°C, and an electro-optic coefficient of 20 pm/V.

Intermolecular Dynamics and Structure in Aqueous Lidocaine Hydrochloride Solutions.

We investigated the intermolecular dynamics and static structure in the aqueous solutions of lidocaine hydrochloride (LDHCl) in the concentration range of [LDHCl] = 0-2.00 M using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES), small- and wide-angle X-ray scattering (SWAXS), and dynamic light scattering (DLS). For the fs-RIKES experiments, the concentration dependence of the difference low-frequency spectra of the aqueous LDHCl solutions relative to the neat water, which was mainly due to the intermolecular vibrations, was characterized using an exponential function with a characteristic concentration of ∼1 M. For the SWAXS experiments, we observed a manifestation of an excess scattering component centered within a range of 8-10 nm-1 in the aqueous LDHCl solutions. The results of Fourier inversion and further deconvolution analyses unambiguously demonstrated that lidocaines assemble into a nanometer-sized micelle-like structure with the innermost core (∼0.3 nm) and outer shell (∼0.5 nm), respectively. The DLS experiments also found nanometer-sized aggregates and further indicated evidence of the clusters of the aggregates. The results of viscosities, densities, and surface tensions of the solutions and the quantum chemistry calculations supported the unique features of the microscopic intermolecular interaction and the micelle-like aggregation.

Electron Density Estimation and Fiber Fuse Simulation in Laser-Irradiated Bulk Glass

To clarify the formation mechanism of periodic nanometer-size cavity structure of a borosilicate glass sample, the free electron density around the exit surface was investigated when it exposed to intense femtosecond laser radiation. The electron density near the edge of the crack on the surface was estimated to be 10²⁰-10²² cm^-3. From this result, the temperature of the irradiated heating area near the edge of the crack was estimated to reach at least about 6,000 K, which was sufficient for the initiation and propagation of the fiber fuse. In this way, periodic nanosized cavities could be formed by fiber fuse propagation starting near the edge of the crack on the exit surface. Next, fiber fuse propagation in the modified zone formed by continuous-wave laser irradiation in a silica glass sample was investigated theoretically by the explicit finite-difference method using the thermochemical SiO_x production model. In the calculation, we assumed the glass to be in an atmosphere and that part (40 mm in length) of the modified zone was heated to a temperature of 2,923 K. The calculated velocities of fiber fuse propagation in the modified zone were in fair agreement with the experimental values observed at 0.514 and 1.064 mm.

Nanocellular foaming of poly (methyl methacrylate) with chlorodifluoromethane (HCFC-22)/CO2 binary mixtures as a model blowing agent

A foaming process for polymethylmethacrylate (PMMA) using a chlorodifluoromethane (HCFC-22) and carbon dioxide (CO2) binary mixture as a blowing agent at 40 MPa and 353.2 K was studied for the production of foams with high porosity and uniformity. HCFC-22 was employed as a model blowing agent because of (1) much larger solubility to polymers than CO2 and (2) well known phase diagram and physicochemical property. HCFC-22/CO2 binary mixtures improved the homogeneity of the cellular structure. The micrometer-sized cell structures seen in the foams with pure CO2 used as blowing agent were decreased in HCFC-22/CO2 binary mixtures. Homogeneous structure with cells from 0.07 µm to 0.35 µm were obtained in the binary mixtures. The binary mixtures were also effective in increasing the cell nucleation density of nanometer-sized cell structures. We were able to determine the optimal composition of HCFC-22/CO2 to coexist the high expansion ratio and homogeneous structure for PMMA foams.

Elucidating the Stability of Single-Chain Polymeric Nanoparticles in Biological Media and Living Cells.

The controlled folding of synthetic polymer chains into single-chain polymeric nanoparticles (SCPNs) of defined size and shape in water is a viable way to create compartmentalized, nanometer-sized structures for a range of biological applications. Understanding the relationship between the polymer’s microstructure and the stability of folded structures is crucial to achieving desired applications. Here, we introduce the solvatochromic dye Nile red into SCPNs and apply a combination of spectroscopic and microscopic techniques to relate polymer microstructure to nanoparticle stability in complex biological media and cellular environments. Our experimental data show that the polymer’s microstructure has little effect on the stability of SCPNs in biological media and cytoplasm of living cells, but only SCPNs comprising supramolecular benzene-1,3,5-tricarboxamide (BTA) motifs showed good stability in lysosomes. The results indicate that the polymer’s microstructure is vital to ensure nanoparticle stability in highly competitive environments: both hydrophobic collapse and a structured interior are required. Our study provides an accessible way of probing the stability of SCPNs in cellular environments and paves the way for designing highly stable SCPNs for efficient bio-orthogonal catalysis and sensing applications.