Formation Of Surface Structures Research Articles

Fluorinated Polyimide as a Novel High‐Voltage Binder for High‐Capacity Cathode of Lithium‐Ion Batteries

AbstractAn increase in the energy density of lithium‐ion batteries has long been a competitive advantage for advanced wireless devices and long‐driving electric vehicles. Li‐rich layered oxide, xLi2MnO3∙(1−x)LiMn1−y−zNiyCozO2, is a promising high‐capacity cathode material for high‐energy batteries, whose capacity increases by increasing charge voltage to above 4.6 V versus Li. Li‐rich layered oxide cathode however suffers from a rapid capacity fade during the high‐voltage cycling because of instable cathode–electrolyte interface, and the occurrence of metal dissolution, particle cracking, and structural degradation, particularly, at elevated temperatures. Herein, this study reports the development of fluorinated polyimide as a novel high‐voltage binder, which mitigates the cathode degradation problems through superior binding ability to conventional polyvinylidenefluoride binder and the formation of robust surface structure at the cathode. A full‐cell consisting of fluorinated polyimide binder‐assisted Li‐rich layered oxide cathode and conventional electrolyte without any electrolyte additive exhibits significantly improved capacity retention to 89% at the 100th cycle and discharge capacity to 223–198 mA h g−1 even under the harsh condition of 55 °C and high charge voltage of 4.7 V, in contrast to a rapid performance fade of the cathode coated with polyvinylidenefluoride binder.

On femtosecond laser shock peening of stainless steel AISI 316

In this paper we report on the competition in metal surface hardening between the femtosecond shock peening on the one hand, and formation of laser-induced periodic surface structures (LIPSS) and surface oxidation on the other hand. Peening of the stainless steel AISI 316 due to shock loading induced by femtosecond laser ablation was successfully demonstrated. However, for some range of processing parameters, surface erosion due to LIPSS and oxidation seems to dominate over the peening effect. Strategies to increase the peening efficiency are discussed.

A Mechanism for Symmetry Breaking and Shape Control in Single-Crystal Gold Nanorods.

The phenomenon of symmetry breaking-in which the order of symmetry of a system is reduced despite manifest higher-order symmetry in the underlying fundamental laws-is pervasive throughout science and nature, playing a critical role in fields ranging from particle physics and quantum theory to cosmology and general relativity. For the growth of crystals, symmetry breaking is the crucial step required to generate a macroscopic shape that has fewer symmetry elements than the unit cell and/or seed crystal from which it grew. Advances in colloid synthesis have enabled a wide variety of nanocrystal morphologies to be achieved, albeit empirically. Of the various nanoparticle morphologies synthesized, gold nanorods have perhaps been the most intensely studied, thanks largely to their unique morphology-dependent optical properties and exciting application potential. However, despite intense research efforts, an understanding of the mechanism by which a single crystal breaks symmetry and grows anisotropically has remained elusive, with many reports presenting seemingly conflicting data and theories. A fundamental understanding of the symmetry breaking process is needed to provide a rational framework upon which future synthetic approaches can be built. Inspired by recent experimental results and drawing upon the wider literature, we present a mechanism for gold nanorod growth from the moments prior to symmetry breaking to the final product. In particular, we describe the steps by which a cuboctahedral seed particle breaks symmetry and undergoes anisotropic growth to form a nanorod. With an emphasis on the evolving crystal structure, we highlight the key geometrical and chemical drivers behind the symmetry breaking process and factors that govern the formation and growth of nanorods, including control over the crystal width, length, and surface faceting. We propose that symmetry breaking is induced by an initial formation of a new surface structure that is stabilized by the deposition of silver, thus preserving this facet in the embryonic nanorod. These new surfaces initially form stochastically as truncations that remove high-energy edge atoms at the intersection of existing {111} facets and represent the beginnings of a {011}-type surface. Crucially, the finely tuned [HAuCl4]:[AgNO3] ratio and reduction potential of the system mean that silver deposition can occur on the more atomically open surface but not on the pre-existing lower-index facets. The stabilized surfaces develop into side facets of the nascent nanorod, while the largely unpassivated {111} facets are the predominant site of Au atom deposition. Growth in the width direction is tightly controlled by a self-sustaining cycle of galvanic replacement and silver deposition. It is the [HAuCl4]:[AgNO3] ratio that directly determines the particle size at which the more open atomic surfaces can be stabilized by silver and the rate of growth in the width direction following symmetry breaking, thus explaining the known aspect ratio control with Ag ion concentration. We describe the evolving surface faceting of the nanorod and the emergence of higher-index facets. Collectively, these observations allow us to identify facet-size and edge-atom effects as a simple fundamental driver of symmetry breaking and the subsequent development of new surfaces in the presence of adsorbates.

Characteristics of hierarchical micro/nano surface structure formation generated by picosecond laser processing in water and air

Laser surface texturing or micro/nano surface structuring in the air has been extensively studied. However, until now, there are very few studies on the characteristics of laser-textured surfaces in water, and there was no reported work on picosecond laser surface micro/nano-structuring in water. In this work, the surface properties of picosecond laser surface texturing in water and air were analysed and compared. 316L stainless steel substrates were textured using a picosecond laser. The surface morphology and the chemical composition were characterised using Philips XL30 FEG-SEM, EDX and confocal laser microscopy. The wettability of the textured surfaces was determined using a contact angle analyser FTA 188. Results showed that a variety of hierarchical micro/nano surface patterns could be controlled by a suitable adjustment of laser parameters. Not only surface morphology but also remarkable differences in wettability, optical reflectivity and surface oxygen content were observed for different types of surface textures produced by laser surface texture in water and air. The possible mechanisms of the changes in the behaviour of laser-textured surfaces are discussed.

Orientation of ripples induced by ultrafast laser pulses on copper in different liquids

Formation of laser-induced periodic surface structures (LIPSS or ripples) was studied on a metallic surface of polished copper by using irradiation with multiple femtosecond laser pulses in different environmental conditions (air, water, ethanol and methanol). Uniform LIPSS have been achieved by controlling the peak fluence and the overlapping rate. Ripples in both orientations, perpendicular and parallel to laser polarization, were observed in all liquids simultaneously. The orientation of these ripples in the center of the ablated line was changing with the incident light intensity. For low intensities the orientation of the ripples is perpendicular to the laser polarization, whereas for high intensities it turns parallel to it without considerable changes in the period. Multi-directional LIPSS formation was also observed for moderate peak fluence in liquid environments.

Laser-Induced Translative Hydrodynamic Mass Snapshots: Noninvasive Characterization and Predictive Modeling via Mapping at Nanoscale

Nanoscale thermally assisted hydrodynamic melt perturbations induced by ultrafast laser energy deposition in noble-metal films produce irreversible nanoscale translative mass redistributions and results in formation of radially-symmetric frozen surface structures. We demonstrate that the final three-dimensional (3D) shape of the surface structures formed after resolidification of the molten part of the film is shown to be governed by incident laser fluence and, more importantly, predicted theoretically via molecular dynamics modeling. Considering the underlying physical processes associated with laser-induced energy absorption, electron-ion energy exchange, acoustic relaxation and hydrodynamic flows, the theoretical approach separating slow and fast physical processes and combining hybrid analytical two-temperature calculations, scalable molecular-dynamics simulations, and a semi-analytical thin-shell model was shown to provide accurate prediction of the final nanoscale solidified morphologies, fully consistent with direct electron-microscopy visualization of nanoscale focused ion-beam cuts of the surface structures produced at different incident laser fluences. Finally, these results are in reasonable quantitative agreement with mass distribution profiles across the surface nanostructures, provided by their noninvasive and non-destructive nanoscale characterization based on energy-dispersive x-ray fluorescence spectroscopy, operating at variable electron-beam energies.

Regulation of the membrane structure by brassinosteroids and progesterone in winter wheat seedlings exposed to low temperature

Steroids constitute one of the most important groups of compounds of regulatory properties both in the animal and plant kingdom. In plants, steroids such as brassinosteroids or progesterone, by binding to protein receptors in cell membranes, regulate growth and initiate processes leading to increased tolerance to stress conditions. Due to their structural similarities to sterols, these steroids may also directly interact with cellular membranes. Our aim was to determine the changes of the structural parameters of lipid membranes under the influence of hydrophobic steroid compounds, i.e., 24-epibrassinolide (EBR) and its precursor—24-epicastasterone (ECS) and progesterone (PRO). Lipids were isolated from wheat seedlings with different tolerances to frost, grown at low temperatures (5 °C) for 1.5 and 3 weeks (acclimation process). Control plants were cultured continuously at 20 °C. From galactolipids and phospholipids, the main polar lipid fractions, the monolayers were formed, using a technique of Langmuir trough. EBR and ECS were introduced into monolayers, together with lipids, whereas the PRO was dissolved in the aqueous sub-phase upon which the monolayers were spread. Measurements performed at 25 °C and 10 °C showed a significant action of the tested compounds on the physicochemical properties of the monolayers. EBR and PRO increased the area per lipid molecule in monolayers, resulting in formation of more flexible surface structures while the presence of the ECS induced the opposite effect. The influence of the polarity of lipids and steroids on the interactions in the monolayer was discussed. Lipids extracted from the membranes of wheat with the most tolerance to frost were characterized by the highest fatty acid unsaturation and steroids had a relatively weak effect on the parameters of the structure of their monolayers.

Effect of extracytoplasmic function sigma factors on autoaggregation, hemagglutination, and cell surface properties of Porphyromonas gingivalis.

Porphyromonas gingivalis is a bacterium frequently isolated from chronic periodontal lesions and is involved in the development of chronic periodontitis. To colonize the gingival crevice, P. gingivalis has to adapt to environmental stresses. Microbial gene expression is regulated by transcription factors such as those in two-component systems and extracytoplasmic function (ECF) sigma factors. ECF sigma factors are involved in the regulation of environmental stress response genes; however, the roles of individual ECF sigma factors are largely unknown. The purpose of this study was to investigate the functions, including autoaggregation, hemagglutination, gingipain activity, susceptibility to antimicrobial agents, and surface structure formation, of P. gingivalis ECF sigma factors encoded by SigP (PGN_0274), SigCH (PGN_0319), PGN_0450, PGN_0970, and SigH (PGN_1740). Various physiological aspects of the sigP mutant were affected; autoaggregation was significantly decreased at 60 min (p < 0.001), hemagglutination activity was markedly reduced, and enzymatic activities of Kgp and Rgps were significantly decreased (p < 0.001). The other mutants also showed approximately 50% reduction in Rgps activity. Kgp activity was significantly reduced in the sigH mutant (p < 0.001). No significant differences in susceptibilities to tetracycline and ofloxacin were observed in the mutants compared to those of the wild-type strain. However, the sigP mutant displayed an increased susceptibility to ampicillin, whereas the PGN_0450 and sigH mutants showed reduced susceptibility. Transmission electron microscopy images revealed increased levels of outer membrane vesicles formed at the cell surfaces of the sigP mutant. These results indicate that SigP is important for bacterial surface-associated activities, including gingipain activity, autoaggregation, hemagglutination, vesicle formation, and antimicrobial susceptibility.

Design of co-existence parallel periodic surface structure induced by picosecond laser pulses on the Al/Ti multilayers

Formation of periodic nanostructures on the Ti/5x(Al/Ti)/Si multilayers induced by picosecond laser pulses is studied in order to better understand the formation of a laser-induced periodic surface structure (LIPSS). At fluence slightly below the ablation threshold, the formation of low spatial frequency-LIPSS (LSFL) oriented perpendicular to the direction of the laser polarization is observed on the irradiated area. Prolonged irradiation while scanning results in the formation of a high spatial frequency-LIPSS (HSFL), on top of the LSFLs, creating a co-existence parallel periodic structure. HSFL was oriented parallel to the incident laser polarization. Intermixing between the Al and Ti layers with the formation of Al-Ti intermetallic compounds was achieved during the irradiation. The intermetallic region was formed mostly within the heat affected zone of the sample. Surface segregation of aluminium with partial ablation of the top layer of titanium was followed by the formation of an ultra-thin Al2O3 film on the surface of the multi-layered structure.

Interaction of slow highly charged ions with a metal surface covered with a thin dielectric film. The role of the neutralization energy in the nanostructures formation

We consider the slow highly charged ions impinging upon a metal surface covered with a thin dielectric film, and formation of the surface nanostructures (craters) from the standpoint of the required energy. For the moderate ionic velocities, the size of the surface features depends on the deposited kinetic energy of the projectile and the ionic neutralization energy. The neutralization energy is calculated by employing the recently developed quasi-resonant two-state vector model for the intermediate Rydberg state population and the micro-staircase model for the cascade neutralization. The electron interactions with the ionic core, polarized dielectric and charge induced on the metal surface are modelled by the appropriate asymptotic expressions and the method for calculation of the effective ionic charges in the dielectric is proposed.The results are presented for the interaction of ions (velocity a.u.; ) with the metal surface (Co) covered with a thin dielectric film, for model values of dielectric constant inside the interaction region. In the absence of dielectric film, the neutralization energy is lower than the potential (ionization) energy due to the incomplete neutralization. The presence of dielectric film additionally decreases the neutralization energy. We calculate the projectile neutralization energy in the perturbed dielectric (perturbation is caused by the ionic motion and the surface structure formation). We correlate the neutralization energy added to the deposited kinetic energy with the experimentally obtained energy necessary for the formation of the nano-crater of a given depth.

In situ probing of pulsed laser melting and laser-induced periodic surface structures formation by dynamic reflectivity

The melting process and nanostructure formation induced by nanosecond and picosecond laser pulses on bulk silicon and copper thin film were studied by ex situ analysis and in situ real time reflectivity. Three different probing wavelengths (633, 473 and 326 nm) were used during the pump laser processing and were correlated to the beam parameters (pulse duration, laser fluence and number of laser shots) and copper thin film thickness. On a silicon surface using a KrF laser beam (27 ns, 1 Hz, 248 nm), the melting threshold was determined close to 700 mJ cm−2 and the melting duration increased from 10 to 130 ns as the fluence increased from 700 to 1750 mJ cm−2. Nanostructures with a spatial period close to the laser wavelength were formed on both copper thin film and silicon substrate after nanosecond Nd:YAG laser (10 ns, 266 nm, 1 Hz) irradiation. In the picosecond regime, using an Nd:YAG laser (40 ps, 266 nm, 1 Hz), different nanostructures, from spikes to laser-induced periodic surface structures, were formed on 500 nm copper thin film and were analyzed with respect to the drop in dynamic reflectivity changes versus the number of laser shots.

Enhancement of surface area and wettability properties of boron doped diamond by femtosecond laser-induced periodic surface structuring

We demonstrate the formation of laser-induced periodic surface structures (LIPSS) in boron-doped diamond (BDD) by irradiation with femtosecond near-IR laser pulses. The results show that the obtained LIPSS are perpendicular to the laser polarization, and the ripple periodicity is on the order of half of the irradiation wavelength. The surface structures and their electrochemical properties were characterized using Raman micro-spectroscopy, in combination with scanning electron and atomic force microscopies. The textured BDD surface showed a dense and large surface area with no change in its structural characteristics. The effective surface area of the textured BDD electrode was approximately 50% larger than that of a planar substrate, while wetting tests showed that the irradiated area becomes highly hydrophilic. Our results indicate that LIPSS texturing of BDD is a straightforward and simple technique for enhancing the surface area and wettability properties of the BDD electrodes, which could enable higher current efficiency and lower energy consumption in the electrochemical oxidation of toxic organics.

Surface modification of ASP 30 steel induced by femtosecond laser with 1014 and 1013 W/cm2 intensity in vacuum

AbstractA study of ASP 30 steel surface modification with high intensity Ti:sapphire laser, operating at 804 nm wavelength and pulse duration of 60 fs, in vacuum ambient, is presented. ASP 30 steel surface variations were studied at laser intensities of 1014 and 1013 W/cm2. The steel target specific surface changes and phenomena observed are: (i) Creation of craters at 1014 W/cm2 intensity; (ii) formation of periodic surface structures only at the reduced intensity of 1013 W/cm2; (iii) chemical surface changes registered only at higher laser intensity, and (iv) occurrence of plasma in front of the surface, including its emission in X-ray region. It can be concluded from this study that the reported laser intensities can effectively be applied for ASP 30 steel surface modification. Careful choosing of laser intensity and pulse count can lead to precise superficial material removal, for example laser intensity ~1013 W/cm2 and low pulse count can lead to ultra-precise surface processing. Generally, femtosecond laser surface modification of ASP 30 steel is non-contact and very rapid compared with traditional modification methods.

Role of nanoparticles generation in the formation of femtosecond laser-induced periodic surface structures on silicon.

An initial roughness is assumed in the most accepted Sipe-Drude model to analyze laser-induced periodic surface structures (LIPSS). However, the direct experimental observation for the crucial parameters is still lacking. The generation of nanoparticles and low-spatial frequency LIPSS (LSFL) (LIPSS with a periodicity close to laser wavelength) on a silicon surface upon a single pulse and subsequent pulses irradiation, respectively, is observed experimentally. Finite-difference time-domain (FDTD) simulation indicates that the nanoparticles generated with the first pulse enhance the local electric field greatly. Based on the experimental extrapolated parameters, FDTD-η maps have been calculated. The results show that the inhomogeneous energy deposition, which leads to the formation of LSFL, is mainly from the modulation of the nanoparticles with a radius of around 100nm.

Real-time in situ study of femtosecond-laser-induced periodic structures on metals by linear and nonlinear optics.

Femtosecond-laser surface structuring on metals is investigated in real time by both fundamental and second harmonic generation (SHG) signals. The onset of surface modification and its progress can be monitored by both the fundamental and SHG probes. However, the dynamics of femtosecond-laser-induced periodic surface structures (FLIPSSs) formation can only be revealed by SHG but not fundamental because of the higher sensitivity of SHG to structural geometry on metal. Our technique provides a simple and effective way to monitor the surface modification and FLIPSS formation thresholds and allows us to obtain the optimal FLIPSS for SHG enhancement.

Formation and Properties of Laser-Induced Periodic Surface Structures on Different Glasses.

The formation and properties of laser-induced periodic surface structures (LIPSS) was investigated on different technically relevant glasses including fused silica, borosilicate glass, and soda-lime-silicate glass under irradiation of fs-laser pulses characterized by a pulse duration τ = 300 fs and a laser wavelength λ = 1025 nm. For this purpose, LIPSS were fabricated in an air environment at normal incidence with different laser peak fluence, pulse number, and repetition frequency. The generated structures were characterized by using optical microscopy, scanning electron microscopy, focused ion beam preparation and Fast-Fourier transformation. The results reveal the formation of LIPSS on all investigated glasses. LIPSS formation on soda-lime-silicate glass is determined by remarkable melt-formation as an intra-pulse effect. Differences between the different glasses concerning the appearing structures, their spatial period and their morphology were discussed based on the non-linear absorption behavior and the temperature-dependent viscosity. The findings facilitate the fabrication of tailored LIPSS-based surface structures on different technically relevant glasses that could be of particular interest for various applications.

Evolution of radius and light scattering properties of single drying microdroplets of colloidal suspension

We report on observation of well-pronounced characteristic features of elastic light scattering of evaporating solution and suspension microdroplet of the anionic surfactant sodium dodecyl sulfate (SDS) and colloidal silica (SiO2) nanospheres in diethylene glycol (DEG) during SDS surface layer and structure formation (crystallization). For pure DEG/SDS solution droplet evaporation process, characteristic evaporation transitions manifested in the evolution of the droplet radius, a(t) for all the SDS concentrations (C = 20 mM, 40 mM and 100 mM) studied as well as well-pronounced intensity signals characterizing SDS soft gel-solid transitions for initial SDS concentrations, C > 40 mM. In the case of microdroplets composed of DEG/SDS with controlled addition of colloidal silica, the intensity fluctuations were enhanced and had profiles dependent on the initial composition of the suspension. Exemplary wet droplets at the initial evaporation stages and final dry aggregates of SDS and SDS/SiO2 were deposited on a substrate and observed with Scanning Electron Microscopy (SEM). Features of the deposited structures correlate well with the elastic scattered light measurements characterizing the drying processes.

Reconstruction of Laser-Induced Surface Topography from Electron Backscatter Diffraction Patterns.

We demonstrate that the surface topography of a sample can be reconstructed from electron backscatter diffraction (EBSD) patterns collected with a commercial EBSD system. This technique combines the location of the maximum background intensity with a correction from Monte Carlo simulations to determine the local surface normals at each point in an EBSD scan. A surface height map is then reconstructed from the local surface normals. In this study, a Ni sample was machined with a femtosecond laser, which causes the formation of a laser-induced periodic surface structure (LIPSS). The topography of the LIPSS was analyzed using atomic force microscopy (AFM) and reconstructions from EBSD patterns collected at 5 and 20 kV. The LIPSS consisted of a combination of low frequency waviness due to curtaining and high frequency ridges. The morphology of the reconstructed low frequency waviness and high frequency ridges matched the AFM data. The reconstruction technique does not require any modification to existing EBSD systems and so can be particularly useful for measuring topography and its evolution during in situ experiments.

Study of the formation of thermochemical laser-induced periodic surface structures on Cr, Ti, Ni and NiCr films under femtosecond irradiation**Presented at the Fundamentals of Laser Assisted Micro- and Nanotechnologies (FLAMN-16) International Symposium (Pushkin, Leningrad oblast, 27 June to 1 July 2016).

The formation of femtosecond laser-induced periodic surface structures (LIPSS’s) on Cr, Ti, Ni and NiCr films (with different Cr contents) is investigated. It is established that thermochemical LIPSS’s with periods of 950, 930 and 980 nm are formed, respectively, on the surfaces of titanium, chromium, and nichrome (with a chromium content of 20%); however, thermochemical LIPSS’s are not formed on the surfaces of nickel and nichrome with a low chromium content, although Raman data indicate that oxidation occurs in all cases. A weakly ordered ablated structure with a period of 250 – 300 nm is found to be formed on oxidised areas of thermochemical LIPSS’s in the case of chromium and nichrome (80/20). Experimental data on selective etching of thermochemical LIPSS’s on titanium and chromium films are presented.

Orthogonally superimposed laser-induced periodic surface structures (LIPSS) upon nanosecond laser pulse irradiation of SiO2/Si layered systems

In this study we examined the formation of laser-induced periodic surface structures (LIPSS) on silicon (Si) in dependence on the thickness of silicon-dioxide (SiO2) on top. LIPSS were generated in air by linearly polarized ≈8 nanosecond laser pulses with a fluence per pulse of 2.41Jcm−2 at a repetition rate of 100kHz. For SiO2 layers <80nm, LIPSS oriented perpendicular to the laser polarization were obtained, but for SiO2 layers >120nm parallel oriented LIPSS were observed. In both cases the periodicity was about 80–90% of the applied laser wavelength (λ0=532nm). By variation of the SiO2 layer thickness in the range between 80nm–120nm, the dominating orientation changes. Even orthogonally superimposed LIPSS with a periodicity of only 60% of the laser wavelength were found. We show that the transition of the orientation direction of LIPSS is related to the penetration depth of surface plasmon polariton (SPP) fields into the oxide layer.