Measuring surface topography with scanning electron microscopy. I. EZEImage: a program to obtain 3D surface data.

Scanning electron microscopy (SEM) is widely used in the science of materials and different parameters were developed to characterize the surface roughness. In a previous work, we studied the surface topography with fractal dimension at low scale and two parameters at high scale by using the variogram, that is, variance vs. step log-log graph, of a SEM image. Those studies were carried out with the FERImage program, previously developed by us. To verify the previously accepted hypothesis by working with only an image, it is indispensable to have reliable three-dimensional (3D) surface data. In this work, a new program (EZEImage) to characterize 3D surface topography in SEM has been developed. It uses fast cross correlation and dynamic programming to obtain reliable dense height maps in a few seconds which can be displayed as an image where each gray level represents a height value. This image can be used for the FERImage program or any other software to obtain surface topography characteristics. EZEImage also generates anaglyph images as well as characterizes 3D surface topography by means of a parameter set to describe amplitude properties and three functional indices for characterizing bearing and fluid properties.     

Hydrothermally etched titanium: a review on a promising mechano-bactericidal surface for implant applications

The growing demand for titanium-based implants and the subsequent rise in implant-associated infections necessitate novel developments in anti-infective technologies. Recent research has drawn inspiration from nature to solve this problem. The nanoscale topography observed on cicada and dragonfly wings serves as a blueprint for synthetic analogs which seek to kill bacteria on contact through mechanical forces. This type of interaction has been dubbed the mechano-bactericidal effect. Various techniques have been utilized to mimic and improve upon these natural bactericidal surfaces. Alkaline hydrothermal etching is a simple and cost-effective technique to fabricate nanoscale protrusions on titanium and its alloys. This review aims to consolidate the current knowledge surrounding how fabrication parameters lead to varying surface topographies on titanium substrates, and subsequently, how surface topography and bacterial characteristics affect bactericidal activity. The bactericidal mechanism of hydrothermally etched titanium is inferred from comparisons with similar mechano-bactericidal biomaterials. The hostility of hydrothermally etched titanium toward bacteria is discussed in contrast to the observed host cell compatibility. Last, suggestions are made for the standardization of terminology in this emerging field.     

Improved oxygen delivery in a continuous-roller-bottle reactor

Variations to the original aeration system in a continuous roller bottle reactor of novel design have been tested and compared for optimal oxygen (O) delivery. Reactor operating parameters that affect O transfer are rotation rate, liquid-volume level, fresh-feed rate, and supplementary-aeration rate. Design modifications to enhance gas-liquid O transfer include the addition of wall baffles and center baffles. The number and location of each of these baffles are compared for their effect on k_La values in the reaction chamber. The liquid feed into the system has been modified to improve the axial liquid mixing and O transfer.     

Control of droplet size and spacing in micrometer-sized polymeric dewetting patterns

When a polymer solution is cast on a flat substrate and the solvent is allowed to evaporate, dewetting might take place. Instead of a continuous film, the polymer forms micrometer-sized droplets. By controlling the solvent casting process with the help of a roller apparatus, the size and spacing of the polymer droplets can be adjusted. We investigated the effect of polymer concentration and roller speed on the pattern dimensions and found that higher concentrations lead to larger polymer droplets (from 1 to 11 microm), whereas faster roller speeds lead to a wider interdroplet spacing (from 4 to 130 microm).     

Transient Changes in Topology and Energy on Extension of Polybutadiene Networks

The theory of elasticity of polymer networks has been developed along two lines. The phenomenological approach leads to the Mooney-Rivlin relation between stress and extension ratio for uniaxial extension. The statistical theory of elasticity, based on a model for polymer molecules, predicts a similar relation with one of the constants zero. Actual elastic properties of rubbers do not agree fully with either theory.

Experimental results are reported obtained with quantitatively cured polybutadiene and polyisoprene vulcanizates. These data are near-equilibrium results through the use of a cyclic stress sequence which largely eliminates the influence of long-time creep. The dependence of the initial modulus and the parameters of the Mooney-Rivlin relation on the chemical nature and the degree of branching of the polymer, the type of cross-links, and temperature has been investigated. A possible relation between the energy component of the elastic force and one of the parameters is discussed.

These results as well as those in the literature refer to irreversible processes. It is proposed that this irreversibility results from friction accompanying slippage of chain entanglements. This mechanism is compatible with the observed dependences. It is concluded that the variation of elastic properties with elongation is due to changes in network topography.

Some observations are made on the topological changes of vulcanizate networks at very high elongations. Similarities are pointed out between reinforcement by stress crystallization and by addition of carbon black. The effect of blacks is attributed mainly to preferential adsorption on the carbon particles of short network chains which become overstressed at high deformation. On adsorption the kinetic energy of these particular chains will be dissipated in the form of heat of adsorption.

Examples are given of the applicability of F. Bueche's relation between extension of the sample and that of the elastomer matrix in a filled vulcanizate. This equation differs from that based on Einstein's relation for the viscosity of suspensions, which has been shown to be applicable in other filled rubbers. The difference between the two relations may be associated with the absence or presence of chemical bonding of elastomer to filler.

Network topography has an influence on the ultimate properties of vulcanizates. Polybutadiene samples in which the cross-links are single bonds break at lower elongation than those with equal concentrations of cross-links consisting of 18-atom chains.     

Monte Carlo study of the topographic effects on the proton binding at the energetically heterogeneous metal oxide/electrolyte interface

The grand canonical Monte Carlo simulations of proton binding at the energetically heterogeneous metal oxide/electrolyte interface are presented. Special attention is focused on the surface topography: distribution of adsorption sites on the surface and adsorption energy among these sites. In addition to the patchwise and random topographies of adsorption energy distributions, the geometrically correlated topography (generalized Gaussian model) is tested. The adsorption isotherms appear to be extremely dependent on the assumed topography; however, this effect becomes complex if we include long-range interactions. So, the two models, one neglecting lateral interactions and another taking them into account, are considered.     

Direct visualization of dewetting of molecularly thin liquid films on solid surfaces

The effect of the surface energy gamma, disjoining pressure, Pi, and roughness on the dewetting of molecularly thin liquid lubricant films on magnetic disks, which have sub-nanometer surface topography, has been investigated by visualizing the dewetting process directly using ellipsometric microscopy. The dewetting process of thin liquids on the rough surface is determined not only by the well-known instability of films, which is determined by the sign of dPi/dh, but also by the sign of Pi and the surface topography of the substrate even if its roughness is of the sub-nanometer order. The dewetting film formed small droplets, which were not along the surface topography of the substrate, when Pi < 0. On the other hand, it formed grooves along the surface topography with a sub-nanometer roughness when Pi > 0. Moreover, the sub-nanometer roughness initiated the dewetting of the metastable liquid thin films.     

Micro-morphological investigations on wettability of Al-incorporated c-Si thin films using statistical surface roughness parameters

The tunable surface properties of Al-incorporated c-Si and/or homogeneous c-Si (i.e., absorber layer) thin films are investigated with the help of 3D surface topography, statistical analysis, and contact angle measurement. The absorber layers are developed by ion irradiation on c-Al/a-Si films, which results the crystallization of Si in bilayer films, and the top unreacted Al layers were chemically etched off by wet selective etching. The 3D surface topography and statistical analysis is performed on the atomic force microscopy images of the absorber film surface. The analyses suggest that the surfaces are highly complex and irregular isotropic. The surface roughness and irregularity is found to be decreasing with increasing ion fluence. Variation of contact angle with statistical parameters suggest that the wettability of the absorber surface strongly depends on the surface statistical parameters. The surfaces are hydrophobic in nature, and hydrophobicity is found to decrease with increasing ion fluence. The hydrophobic nature of low reflective absorber surface suggests that the film may be useful as a photon absorber layer for advance solar cell applications.     

Solvent effects on charge transfer bands of nitrogen-centered intervalence compounds

Electron transfer parameters are extracted from the optical spectra of intervalence bis(hydrazine) radical cations. Compounds with 2-tert-butyl-3-phenyl-2,3-diazabicyclo[2.2.2]octyl-containing charge-bearing units that are doubly linked by 4-sigma-bond and by 6-sigma-bond saturated bridges are compared with ones having tert-butylisopropyl- and diphenyl-substituted charge bearing units and others having the aromatic units functioning as the bridge. Solvent effect studies show that the optical transition energy (E(op)) does not behave as dielectric continuum theory predicts but that solvent reorganization energy may be usefully separated from the vibrational reorganization energy by including linear terms in both the Pekar factor (gamma) and the Gutmann donor number (DN) in correlating the solvent effect. Solvation of the bridge for these compounds is too large to ignore, which makes dielectric continuum theory fail to properly predict solvent effects on either E(op) or the free energy for comproportionation.     

Microtopography based on inverse opal structures regulates the behavior of bone marrow‐derived mesenchymal stem cells

Physical cues from the extracellular microenvironment play an important role in regulating cell behavior, such as adhesion, migration, and differentiation. Many studies have shown that different physical parameters (eg, stiffness and topography) could modulate the in vitro differentiation of mesenchymal stem cells (MSCs), which had multilineage differentiation potential and could be easily isolated from various tissues such as bone marrow, adipose tissue, and the umbilical cord. However, the underlying mechanism of the topographical influence on MSCs and the detailed cell‐substrate interaction remain unclear. Here, we present oriented elliptical inverse opal structures for regulating the morphology and alignment of bone marrow‐derived MSCs. The inverse opal structures were made through a convenient bottom‐up approach of self‐assembly, which is facile and cost effective. MSCs cultured on the oriented structures were highly aligned and extended highly oriented thick lamellipodia. Moreover, the oriented substrates cracked along the lateral boundary of the cells, suggesting that a strong cell‐substrate interaction was induced by the response of MSCs to the oriented topography. These features of the oriented elliptical topography indicated their promising value in stem cell research and tissue engineering.     

Brownian dynamics simulations of polyelectrolyte adsorption onto topographically patterned surfaces

The effect of patterned surface topography on the adsorption of single polyelectrolyte molecules is explored using Brownian dynamics simulations. The polyelectrolyte is modeled as a free-draining, freely jointed bead-rod chain, and electrostatic interactions are incorporated using a screened Coulombic potential with excluded volume interactions accounted for by the repulsive part of a Lennard-Jones potential. Topography consisting of periodically spaced valleys of square cross section separated by flat hills is considered. Chain conformations are characterized for a wide range of valley widths, depths, and spacings as well as for several different types of surface charge distributions. Depending on the parameter values describing the topography, the chains are found to adopt conformations ranging from flat and extended to those associated with bridge-, brush-, or semi-bridge-like structures. The formation of these structures is rationalized on the basis of a free-energy model that takes into account the increase in free energy due to entropic confinement, excluded volume interactions, and chain stretching as well as the decrease in free energy due to bead-surface electrostatic attraction. The results of this work are expected to be useful in designing patterned surface topography to control the conformations of adsorbed polyelectrolyte molecules.     

Analysis of roller pen inks by capillary zone electrophoresis

The analysis of roller pen inks has become more and more important in fraudulent document examination because of the extensive use of roller pens in financial documents. Capillary electrophoresis with powerful resolution was applied for the analysis of roller pen inks. The experiment focused on the optimization of the separation of the extract from commercially available roller pen entries. A better separation electropherogram was obtained when a 20 mM borate buffer at pH 8.5 and a fused silica capillary with an inner diameter of 100 μm with a total length of 47 (40 cm to the detector window) were used. Five inks from roller pens of different manufacturers and countries were analyzed, and their electropherograms showed that most patterns are distinctly different from each other. Capillary with inner diameter of 100 μm increased the intensity of determination; therefore, color dyes were identified in the visible range and were able to provide more information for comparing types of roller pen inks.     

Experimental study of copper leveling additives and their wafer and pattern-scale effect on copper planarization

The impact of Cu leveling additives on electrodeposited Cu topography and subsequent planarization behaviour was studied on both the pattern and wafer scales. The leveling agent significantly reduces as-deposited Cu topography, especially “mounding”. The reduction in topography results in a higher effective Cu removal rate during subsequent Cu planarization, both at the pattern and wafer scales. On the wafer scale, this effect is more evident for lower overburdens as the topography must be eliminated in a shorter total polish time. For Cu electrodeposited from leveler additive-free chemistries, significant pattern-scale topography persists throughout almost the entire planarization process, whereas for Cu deposited using a leveling agent only very wide features (～ > 100 μm) show any significant topography evolution during Cu polish. It is shown that excess electrodeposited Cu topography can lead to poor in-plane Cu wiring leakage performance.     

Inverse gas chromatographic investigation of the active sites related to CO adsorption over Rh/SiO2 catalysts in excess of hydrogen

In the present work, the novel methodology of reversed-flow gas chromatography (RF-GC) is extended in a topic of contemporary scientific and technological interest, such as the effect of hydrogen in the "topography" of the active sites related to CO adsorption. This study concerns CO adsorption on a silica-supported Rh catalyst, at 90 degrees C. The topography of the catalyst in the absence of hydrogen consists of both randomly and islands of CO bound over chemisorbed CO molecules. In contrast, under H2-rich conditions, the observed topography is almost entirely patchwise ascribed to long-range lateral attractions between adsorbate molecules. In excess of hydrogen, CO adsorption is shifted at higher lateral attractions values which correspond to weaker adsorbate-adsorbent interactions and lower surface coverage. This provides an indication of a H2-induced desorption, which can be attributed to the formation of an H-CO complex desorbing from the catalyst surface below the temperature required for CO desorption, in the absence of H2, and it may explain the well-known enhancement of the rate of selective CO oxidation in excess of hydrogen by H2.     

Porous Microstructured Surfaces with pH‐Triggered Antibacterial Properties

New antibacterial films are designed with the capability to reversibly regulate their killing and repelling functions in response to variations in environmental pH. These systems consist of porous polystyrene surfaces as the main components and a copolymer bearing pH‐sensitive thiazole and triazole groups as the minor components. These pH‐sensitive groups, located on the surfaces, can be partially protonated at acidic pH levels, increasing the positive charge density of the surfaces and their antibacterial activity. Similarly, their bacterial adhesion and killing efficiencies in response to changes in pH are evaluated by analyzing the bacterial viability of Staphylococcus aureus bacteria on the surfaces under acidic and neutral pH values. It is demonstrated that after only 1 h of incubation with the bacterial suspension in acidic conditions, the surfaces killed the bacteria, while at pH = 7.4, some of the adhered bacteria are removed. Furthermore, the surface topography exerts an important role by intensifying this response.     

辊速辊温对高密度聚乙烯拉伸微孔膜及其片晶结构的影响

采用熔融挤出片材—退火—冷拉伸—热拉伸—热定形的方法来制备高密度聚乙烯(HDPE)微孔膜,利用FTIR、SEM和DSC等测试方法来研究辊速辊温对HDPE拉伸微孔膜及其片晶结构的影响.研究结果表明,所选树脂的分子量、分子量分布以及弛豫时间能够满足现有加工条件,形成片晶取向度较高的预制膜;在相同辊温下,随辊速增加,退火前预...     

Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole‐2‐ylidene Ligands

The reactivity of benzimidazol‐2‐ylidenes with respect to gold nanoparticles (AuNPs) has been investigated using a combined experimental and computational approach. First, the grafting of benzimidazol‐2‐ylidenes bearing benzyl groups on the nitrogen atoms is described, and comparisons are made with structurally similar N‐heterocyclic carbenes (NHCs) bearing other N‐groups. Similar reactivity was observed for all NHCs, with 1) the erosion of the AuNPs under the effect of the NHC and 2) the formation of bis(NHC) gold complexes. DFT calculations were performed to investigate the modes of grafting of such ligands, to determine adsorption energies, and to rationalize the spectroscopic data. Two types of computational models were developed to describe the grafting onto large or small AuNPs, with either periodic or cluster‐type DFT calculations. Calculations of NMR parameters were performed on some of these models, and discussed in light of the experimental data.     

Molecular mechanics (MM2) and conformational analysis of compounds with N?C?O units. Parametrization of the force field and anomeric effect

A molecular mechanics force field was developed for systems bearing the N? C? O unit on the basis of 6-31G* and 4-21G “ab initio” calculations with full optimization of the geometry and experimental heats of formation. The parameters used, which implicitly included the anomeric effect, provided good geometric and energetic results, both for the compounds on which the parametrization was based and for others on which the validity of the predictions was checked.     

Entropically Driven Self‐Assembly of Bolaamphiphilic Perylene Dyes in Water

The specific hydrophobic effect involved in the self‐assembly of a bolaamphiphilic perylene bisimide (PBI) dye bearing oligoethylene glycol (OEG) chains has been identified. In pure water, the self‐assembly is entropically driven and enthalpically disfavored, as explored by optical spectroscopy and isothermal titration calorimetry studies. Besides strong π–π interactions between the PBI units that are primarily of enthalpic nature, the major contribution to the self‐assembly is the gain of entropy by release of confined water molecules from the hydration shell of the hydrophilic OEG moieties. Both contributions favor self‐assembly, but their countervailing thermodynamic parameters are reflected in an uncommon temperature dependence, which can be inverted upon gradual addition of an organic cosolvent that makes the π–π interaction increasingly dominant.     

The concept of constant emission yield in GDOES

This review paper describes the evolution of the quantification procedure for compositional depth profiling (CDP) in glow discharge optical emission spectrometry (GD-OES), based on the constant emission yield concept. The concept of emission yield (EY) is defined and ways of measuring it experimentally are discussed. The history of the development of quantitative CDP is reviewed, which shows that all of the different approaches depend on the assumption that the EY is essentially a matrix-independent quantity. Particular emphasis is placed on the dependence of the EY on the plasma parameters of current, voltage, power and pressure. In short, impedance changes (current voltage) can significantly affect the emission yield and should either be corrected mathematically or the impedance should be kept constant by pressure regulation in order to obtain reliable results from GDOES CDP. On the other hand, the effect of varying the pressure on the emission yield can be considered to be minor within the limits of practical operating conditions for most CDP applications. It is worth, however, bearing in mind that varying the discharge pressure has a significant effect on the plasma processes, and does affect the emission yield when these variations are large. The experimental results obtained for the emission yield are related to the results from theoretical model calculations published on the subject.