Analytical Surface Research Articles

Detailed quasiclassical dynamics of the F- + CH3Br reaction on an ab initio analytical potential energy surface.

Dynamics and mechanisms of the F- + CH3Br(v = 0) → Br- + CH3F (SN2 via Walden inversion, front-side attack, and double inversion), F- + inverted-CH3Br (induced inversion), HF + CH2Br- (proton abstraction), and FH⋯Br- + 1CH2 reactions are investigated using a high-level global ab initio potential energy surface, the quasiclassical trajectory method, as well as non-standard configuration- and mode-specific analysis techniques. A vector-projection method is used to identify inversion and retention trajectories; then, a transition-state-attack-angle-based approach unambiguously separates the front-side attack and the double-inversion retention pathways. The Walden-inversion SN2 channel becomes direct rebound dominated with increasing collision energy as indicated by backward scattering, initial back-side attack preference, and the redshifting of product internal energy peaks in accord with CF stretching populations. In the minor retention and induced-inversion pathways, almost the entire available energy transfers into product rotation-vibration, and retention mainly proceeds with indirect, slow double inversion following induced inversion with about 50% probability. Proton abstraction is dominated by direct stripping (evidenced by forward scattering) with CH3-side initial attack preference, providing mainly vibrationally ground state products with significant zero-pointenergy violation.

New analytical methods using carbon-based nanomaterials for detection of Salmonella species as a major food poisoning organism in water and soil resources

Salmonella is one of the most prevalent causing agents of food- and water-borne illnesses, posing an ongoing public health threat. These food-poisoning bacteria contaminate the resources at different stages such as production, aggregation, processing, distribution, as well as marketing. According to the high incidence of salmonellosis, effective strategies for early-stage detection are required at the highest priority. Since traditional culture-dependent methods and polymerase chain reaction are labor-intensive and time-taking, identification of early and accurate detection of Salmonella in food and water samples can prevent significant health economic burden and lessen the costs. The immense potentiality of biosensors in diagnosis, such as simplicity in operation, the ability of multiplex analysis, high sensitivity, and specificity, have driven research in the evolution of nanotechnology, innovating newer biosensors. Carbon nanomaterials enhance the detection sensitivity of biosensors while obtaining low levels of detection limits due to their possibility to immobilize huge amounts of bioreceptor units at insignificant volume. Moreover, conjugation and functionalization of carbon nanomaterials with metallic nanoparticles or organic molecules enables surface functional groups. According to these remarkable properties, carbon nanomaterials are widely exploited in the development of novel biosensors. To be specific, carbon nanomaterials such as carbon nanotubes, graphene and fullerenes function as transducers in the analyte recognition process or surface immobilizers for biomolecules. Herein the potential application of carbon nanomaterials in the development of novel Salmonella biosensors platforms is reviewed comprehensively. In addition, the current problems and critical analyses of the future perspectives of Salmonella biosensors are discussed.

A Surface Potential Model for Field-Effect Transistors With Bound-Charge Engineering

Semiconductor doping is limited by such practical concerns as bandgap narrowing and solid solubility limits of dopants. Bound-charge engineering (BCE) bypasses these limits by doping with surface bound charge located on the interface between a semiconductor and an adjacent low-permittivity oxide; it can be used to reduce depletion lengths of junctions in field-effect transistors (FETs). BCE is established by basic electrostatics and is widely applicable to emerging materials and novel devices. In this work, an analytical surface potential model for gate-all-around BCE-assisted silicon nanowire FETs, with arbitrary and possibly distinct spacer and gate oxides, is derived. This model is based on scaling theory and verified against atomistic quantum transport simulations; it provides an intuitive formalism for developing and modeling devices with BCE.

Algorithm for the Conformal 3D Printing on Non-Planar Tessellated Surfaces: Applicability in Patterns and Lattices

In contrast to the traditional 3D printing process, where material is deposited layer-by-layer on horizontal flat surfaces, conformal 3D printing enables users to create structures on non-planar surfaces for different and innovative applications. Translating a 2D pattern to any arbitrary non-planar surface, such as a tessellated one, is challenging because the available software for printing is limited to planar slicing. The present research outlines an easy-to-use mathematical algorithm to project a printing trajectory as a sequence of points through a vector-defined direction on any triangle-tessellated non-planar surface. The algorithm processes the ordered points of the 2D version of the printing trajectory, the tessellated STL files of the target surface, and the projection direction. It then generates the new trajectory lying on the target surface with the G-code instructions for the printer. As a proof of concept, several examples are presented, including a Hilbert curve and lattices printed on curved surfaces, using a conventional fused filament fabrication machine. The algorithm’s effectiveness is further demonstrated by translating a printing trajectory to an analytical surface. The surface is tessellated and fed to the algorithm as an input to compare the results, demonstrating that the error depends on the resolution of the tessellated surface rather than on the algorithm itself.

Quasi-local photon surfaces in general spherically symmetric spacetimes

Based on the geometry of the codimension-2 surface in general spherically symmetric spacetime, we give a quasi-local definition of a photon sphere as well as a photon surface. This new definition is the generalization of the one provided by Claudel, Virbhadra, and Ellis but without referencing any umbilical hypersurface in the spacetime. The new definition effectively excludes the photon surface in spacetime without gravity. The application of the definition to the Lemaître–Tolman–Bondi (LTB) model of gravitational collapse reduces to a second order differential equation problem. We find that the energy balance on the boundary of the dust ball can provide one of the appropriate boundary conditions to this equation. Based on this crucial investigation, we find an analytic photon surface solution in the Oppenheimer–Snyder (OS) model and reasonable numerical solutions for the marginally bounded collapse in the LTB model. Interestingly, in the OS model, we find that the time difference between the occurrence of the photon surface and the event horizon is mainly determined by the total mass of the system but not the size or the strength of the gravitational field of the system.

SpheCow: Flexible dynamical models for galaxies and dark matter haloes

Simple but flexible dynamical models are useful for many purposes, including serving as the starting point for more complex models or numerical simulations of galaxies, clusters, or dark matter haloes. We present SpheCow, a new light-weight and flexible code that allows one to easily explore the structure and dynamics of any spherical model. Assuming an isotropic or Osipkov-Merritt anisotropic orbital structure, the code can automatically calculate the dynamical properties of any model with either an analytical density profile or an analytical surface density profile as starting point. We have extensively validated SpheCow using a combination of comparisons to analytical and high-precision numerical calculations, as well as the calculation of inverse formulae. SpheCow contains readily usable implementations for many standard models, including the Plummer, Hernquist, NFW, Einasto, Sérsic, and Nuker models. The code is publicly available as a set of C++ routines and as a Python module, and it is designed to be easily extendable, in the sense that new models can be added in a straightforward way. We demonstrate this by adding two new families of models in which either the density slope or the surface density slope is described by an algebraic sigmoid function. We advocate the use of the SpheCow code to investigate the full dynamical structure for models for which the distribution function cannot be expressed analytically and to explore a much wider range of models than is possible using analytical models alone.

A probabilistic rainfall model to estimate the leading-edge lifetime of wind turbine blade coating system

Rain-induced leading-edge erosion of wind turbine blades is associated with high repair and maintenance costs. For efficient operation and maintenance, erosion models are required that provide estimates of blade coating lifetime at a real scale. In this study, a statistical rainfall model is established that describes probabilistic distributions of rain parameters that are critical for site-specific leading-edge erosion assessment. A new droplet size distribution (DSD) is determined based on two years’ onshore rainfall data of an inland site in the Netherlands and the obtained DSD is compared with those from the literature. Joint probability distribution functions of rain intensities and droplet sizes are also established for this site as well as for a coastal site in the Netherlands. Then, the application of the proposed model is presented for a 5 MW wind turbine, where the model is combined with wind statistics along with an analytical surface fatigue model that describes lab-scale coating degradation. The expected lifetime of the blade coating is found three to four times less for the wind turbine operating at the coastal site than for the inland site - primarily due to rainfall at higher wind speeds. Further, the robustness of the proposed model is found consistent with varying data periods used for the analyses.

Performance Improvement of Nanoscale Field Effect Diode (FED) with Modified Charge Channel: 2D Simulation and an Analytical Surface Potential Model

Performance Improvement of Nanoscale Field Effect Diode (FED) with Modified Charge Channel: 2D Simulation and an Analytical Surface Potential Model

Mapping Adsorbates with Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy to Understand Rapid Superconformal Filling of Cu Trenches

Additive adsorbates are widely used as surfactants to guide morphological and microstructural evolution during electrochemical deposition of thin films. Even though this strategy has been employed for several decades understanding of the mechanisms at play on the interface remain limited. Modern spectroelectrochemical methods, from surface-enhanced Raman spectroscopy (SERS) to surface-enhanced infrared spectroscopy (SEIRAS) and non-linear optical methods like sum frequency generation (SFG) can provide significant insight into the composition, structure, and dynamics of the surfactant adsorbates through their vibrational signatures. on nominally static surfaces. Each strategy is limited to specimen geometry; SERS is closely linked to the use of rough, plasmonically-active surfaces while SEIRAS measurements are constrained to thin, IR-transparent, metallic films. In the last decade, a significant advance was the introduction of nanoparticle reporters, based largely on silica coated Au nanoparticles, that enable Raman spectroscopy studies on well-defined, single-crystal surfaces whereby the nanoparticle serves to channel the plasmonic energy to the nanoparticle-substrate interface. The silica or alternative coating materials are designed to be inert with respect to the chemistry of the adsorbate species under study while remaining thin enough to allow effective focusing of the optical energy. This approach has been adopted by several researchers interested in understanding molecular adsorption on well-defined, single-crystal surfaces, the electrical double layer, and numerous aspects of reactivity related to catalysis, batteries, electrodeposition, etc. The present work demonstrates the use of Au@SiO2 (core-shell) nanoparticles, also known as SHINERS (Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy), to enable in situ vibrational spectroscopic measurements during electroplating of comparatively smooth, rapidly advancing, surfaces. In particular, the ability of the reporters to float on an advancing surface while responding to area change is used to reveal important, area-driven changes in adsorbate coverage. This study also opens a new avenue for exploring the intersection of analytical surface chemistry and composite electroplating. Figure 1

Analytical 3D Surface Potential Model of a Junction-Based Triple-Gate MOSFET Device

In this paper, a 3D potential model for a triple-gate Si MOSFET is derived in weak inversion using the variable separation technique based on a perimeter weighted approach. The channel potential is solved from Poisson’s equation along two different planes of the device separately and then using the same variable separation technique and proper boundary conditions 3D potential is addressed. Hence, the solution is not directly obtained from 3D Poisson's equation and does not involve any complex computation. The I-V model of the device is then predicted using the drift-diffusion technique. The accuracy of the model is checked with respect to commercial TCAD simulation results, and good agreement is observed. Our proposed model considers short-channel effects but does not find any quantum mechanical effects. The model result has also been compared with the industry-standard model to validate its performance. Due to its good accuracy, the model can be potentially invoked into a numerical simulator to predict the device's electrical behavior.

Double fingerprint characterization of uracil and 5-fluorouracil

Time Resolved Raman spectroelectrochemistry (TR-Raman-SEC) has been used for the first time to obtain two different Raman spectra of one single analyte in the same experiment. This double detection has been accomplished thanks to the use of electrochemical surface enhanced Raman scattering (EC-SERS) and electrochemical surface oxidation enhanced Raman scattering (EC-SOERS) in the same experiment. These two Raman enhancement phenomena can provide a broad insight into the interaction between analyte and substrate surface when they are combined. To prove the possibilities of this methodology, a Raman spectroelectrochemistry study of uracil (U) and 5-fluorouracil (5-FU), two analytes with relevance in medicine and biochemistry, have been performed. Density functional theory (DFT) calculations has been carried out to shed more light on the interaction of these molecules with silver substrates in acidic media.

Development of ESAT-6 Based Immunosensor for the Detection of Mycobacterium tuberculosis.

Early secreted antigenic target of 6 kDa (ESAT-6) has recently been identified as a biomarker for the rapid diagnosis of tuberculosis. We propose a stable and reusable immunosensor for the early diagnosis of tuberculosis based on the detection and quantification of ESAT-6 via cyclic voltammetry (CV). The immunosensor was synthesized by polymerizing aniline dispersed with the reduced graphene oxide (rGO) and Ni nanoparticles, followed by surface modification of the electroconductive polyaniline (PANI) film with anti-ESAT-6 antibody. Physicochemical characterization of the prepared materials was performed by several analytical techniques, including FE-SEM, EDX, XRD, FT-IR, Raman, TGA, TPR, and BET surface area analysis. The antibody-modified Ni-rGO-PANI electrode exhibited an approximately linear response (R2 = 0.988) towards ESAT-6 during CV measurements over the potential range of -1 to +1 V. The lower detection limit for ESAT-6 was approximately 1.0 ng mL-1. The novelty of this study includes the development of the reusable Ni-rGO-PANI-based electrochemical immunosensor for the early diagnosis of tuberculosis. Furthermore, this study successfully demonstrates that electro-conductive PANI may be used as a polymeric substrate for Ni nanoparticles and rGO.

Simulation of methane steam reforming in a catalytic micro-reactor using a combined analytical approach and response surface methodology

In this study, a steady-state analytical model for heat and mass transfer in a 2D micro-reactor coated with a Nickel-based catalyst is developed to investigate microscale hydrogen production. Appropriate correlations for each species’ net rate of production or consumption, mass diffusivity, and the heat of reactions are developed using a detailed reaction mechanism of methane steam reforming. The energy and species conservation equations are then solved for the reactive mixture coupled with the wall energy equation. Finally, the response surface methodology (RSM) is employed to study the effects of channel height, inlet velocity and temperature, wall thickness and conductivity, and external heat flux on CH4 conversion. It is found that the inlet gas temperature, among different parameters, has the most influence on the overall performance of the microchannel hydrogen production. Also, the maximum necessary heat of reforming reaction increases by 84% and 26% if the CH4 conversion changes from 50% to 60% and 60% to 70%, respectively. The developed analytical simulation can be a useful tool for designing experiments in micro-scale hydrogen production.

Simple, general, realistic, robust, analytic tokamak equilibria. Part 2. Pedestals and flow

Part 1 described a wide range of analytic tokamak equilibria modelling smooth limiter surfaces, double- and single-null divertor surfaces, arbitrary aspect ratio, elongation, triangularity and beta. Part 2 generalizes the analysis to further include edge pedestals and toroidal flow. Specifically, edge pedestals are allowed in the pressure, pressure gradient and toroidal current density. Also, an edge-localized contribution to the bootstrap current is treated. In terms of flow, analytic solutions are obtained for two cases: a $\gamma = 2$ adiabatic and a $\gamma = \infty $ incompressible energy conservation relation.

Quantifying Analyte Surface Densities and Their Distribution with Respect to Electromagnetic Hot Spots in Plasmon-Enhanced Spectroscopic Biosensors

Nanoplasmonic sensors based on surface-enhanced spectroscopies carry profound promise toward ultrasensitive detection of biomolecular analytes within miniaturized measurement footprints. High sensitivity in these sensors is achieved by intense electromagnetic (EM) enhancements at hot spots and colocalization of analytes with such hot spots. However, EM hot spots exhibiting high EM enhancements often present confined areas that render them inaccessible to large analytes such as biomolecules. Addressing this requires rational engineering of a nanoplasmonic interface that factors in the analyte surface concentrations and how they are distributed with respect to the EM hot spots. Here we demonstrate combination of metal-enhanced fluorescence (MEF) with a quartz crystal microbalance (QCM) through fabrication of highly resolved plasmonic nanoarrays directly on the QCM sensor. QCM and MEF are simultaneously employed to monitor in situ, real-time binding of fluorescently labeled protein to receptor-functionalized plasmonic arrays. The correlation between the QCM and MEF responses is used to quantify surface density of protein that contributes to the MEF signal intensities and obtain analyte distribution with respect to the EM hot spots by geometric modeling. Results further reveal the MEF assays to be sensitive down to ∼2 zmol of protein within measurement footprints that are 8 orders of magnitude smaller than that of the QCM.

Modeling and design optimization of reclaimed asphalt pavement containing crude palm oil using response surface methodology

This study discusses the influence of using crude palm oil in hot mix asphalt incorporating recycled asphalt pavement materials. The effect of different percentages of recycled asphalt pavement (RAP) and crude palm oil (CPO) on stability, flow, stiffness, voids in mix (VIM), voids filled with asphalt (VFA), and Indirect Tensile Strength (IDT) were assessed. In addition, for the statistical analysis an analytical tool response surface methodology (RSM) was used for designing and statistically analyzing the experimental results. A microstructure level investigation on the virgin binder (60/70) and RAP binder incorporating crude palm oil was performed using atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) analysis. Experimental results showed that stability and indirect tensile strength increases with an increase in recycled asphalt pavement material up till 80%. However, 100% RAP with crude palm oil resulted in reduction in these strength parameters. The microstructural analysis shows that the incorporation of CPO in virgin and RAP aged binder change the structure of aged and virgin binder by new and unique phase formations. The statistical models were found significant and well fitted on bases of R2 value (>0.80), high adequate precision value (>4), low p-value and insignificant lack-of-fit. Furthermore, ANOVA model theoretical results by the RSM analysis were validated by experiments with <5% of error that represent a good agreement between experimental and theoretical results. Crude palm oil inclusion in HMA-RAP showed good improvement in performance parameters indicating a potential source of rejuvenating agent as bio binder material for the pavement construction industry.

Haptic Manipulation of 3D Scans for Geometric Feature Enhancement.

Localisation of geometric features like holes, edges, slots, etc. is vital to robotic planning in industrial automation settings. Low-cost 3D scanners are crucial in terms of improving accessibility, but pose a practical challenge to feature localisation because of poorer resolution and consequently affect robotic planning. In this work, we address the possibility of enhancing the quality of a 3D scan by a manual ’touch-up’ of task-relevant features, to ensure their automatic detection prior to automation. We propose a framework whereby the operator (i) has access to both the actual work-piece and its 3D scan; (ii) evaluates the missing salient features from the scan; (iii) uses a haptic stylus to physically interact with the actual work-piece, around such specific features; (iv) interactively updates the scan using the position and force information from the haptic stylus. The contribution of this work is the use of haptic mismatch for geometric update. Specifically, the geometry from the 3D scan is used to predict haptic feedback at a point on the work-piece surface. The haptic mismatch is derived as a measure of error between this prediction and the real interaction forces from physical contact at that point on the work-piece. The geometric update is driven until the haptic mismatch is minimised. Convergence of the proposed algorithm is first numerically verified on an analytical surface with simulated physical interaction. Error analysis of the surface position and orientations were also plotted. Experiments were conducted using a motion capture system providing sub-mm accuracy in position and a 6 axis F/T sensor. Missing features are successfully detected after the update of the scan using the proposed method in an experiment.

Interface trap charge-based reliability assessment of high-k dielectric-modulated nanoscaled FD SOI MOSFET for low power digital ICs: Modeling and simulation

This paper proposes the analytical surface potential and threshold-voltage model for performance investigation of gate stack (GS) dual-metal-insulated-gate (DMIG) source-engineered (SE) Fully-depleted silicon-on-insulator (FD SOI) MOSFET for low-power digital applications. In which, a new concept of dielectric-modulated high-k insulator-gap with source engineering has been analytically formulated for the first time in dual-metal-gate technology-based FD SOI MOSFET. The surface potential model is developed using two-dimensional Poisson's equations with including effects of interface trap charges (ITCs) and verified against numerical simulations over the TCAD tool from Silvaco ATLAS™. Also, the parametric analysis has been performed to optimize the device dimensions for better nanoscaled MOS design. Further, a six transistor (6-T) SRAM cell is designed using n/p-GS-DMIG SE FD SOI MOSFET for the analysis of static-noise-margin (SNM). It is observed that the proposed FD SOI MOSFET offers excellent immunity towards short-channel-effects (SCEs) along with improved SRAM circuit performance at different ITC conditions. • Impact of interface Trap Charges (ITCs) on GS-DMIG SE FD SOI MOSFET. • Analytical Modeling of Surface Potential and Threshold Voltage of GS-DMIG SE FD SOI MOSFET. • Analysis of DIBL effect at different ITC Conditions. • Comparative analysis of proposed FD SOI MOSFET in nanoscale regime. • Design and Analysis of 6T-SRAM cell using n-/p-GS-DMIG SE FD SOI with including effects of ITCs.

Spatial Analytical Surface Structure Mapping for Three-dimensional Micro-shaped Si by Micro-beam Reflection High-energy Electron Diffraction

Spatial Analytical Surface Structure Mapping for Three-dimensional Micro-shaped Si by Micro-beam Reflection High-energy Electron Diffraction

The Interface Characterization of 2-Mercapto-1-methylimidazole Corrosion Inhibitor on Brass

This work presents a detailed surface analytical study and surface characterization, with an emphasis on the X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses of 2‑mercapto‑1‑methylimidazole (MMI) as a corrosion inhibitor for brass. First, the electrochemical measurements demonstrated a corrosion inhibition effect of MMI in a 3 wt.% NaCl solution. Next, the formation of the MMI surface layer and its properties after 1 month of immersion was analyzed with attenuated total reflectance–Fourier-transform infrared spectroscopy, atomic force microscopy, field-emission scanning electron microscopy, and contact angle analysis. Moreover, to gradually remove the organic surface layer, a gas cluster ion beam (GCIB) sputtering source at different accelerated voltages and cluster sizes was employed. After each sputtering cycle, a high-resolution XPS analysis was performed. Moreover, an angle‑resolved XPS analysis was carried out for the MMI-treated brass sample to analyze the heterogeneous layered structure (the interface of the MMI organic/inorganic brass substrate). The interface properties were also investigated in detail using ToF-SIMS for spectra measurements and 2D imaging. Special attention was devoted to the possible spectral interferences for MMI‑related species. The thermal stability of different MMI-related species using molecular-specific signals without possible spectral interferences was determined by performing a cooling/heating experiment associated with ToF-SIMS measurements. It was shown that these species desorbed from the brass surface in the temperature range of 310–370 °C.