Shapelet-based orientation and defect identification method for nanostructured surface imaging.

Structure-property relations are of fundamental importance for continued progress in materials research. Determining these relationships for nanomaterials introduces additional challenges, especially when nanostructure is present, either through self-assembly or nano-lithographic processes. Recent advances have been made for quantification of nanostructured surfaces, for which many robust experimental imaging methods exist. One promising approach is based on the use ofshapelet functionsfor image analysis, which may be used as a reduced basis for surface pattern structure resulting from a broad range of phenomena (e.g. self-assembly). These shapelet-based methods enable automated quantification of nanostructured images, guided by the user/researcher, providing pixel-level information of local order without requiring detailed knowledge of order symmetries. In this work, enhancements to the existing shapelet-basedresponse distance methodare developed which enable further analysis of local order, including quantification oflocal orientationand identification oftopological defects. The presented shapelet-based methods are applied to a representative set of images of self-assembled surfaces from experimental characterization techniques including scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. These methods are shown to be complementary in implementation and, importantly, provide researchers with a robust and generalized computational approach to comprehensively quantify nanostructure order, including local orientation and boundaries within well-aligned grains.

A generalized shapelet-based method for analysis of nanostructured surface imaging.

The determination of quantitative structure-property relations is a vital but challenging task for nanostructured materials research due to the presence of large-scale spatially varying patterns resulting from nanoscale processes such as self-assembly and nano-lithography. Focusing on nanostructured surfaces, recent advances have been made in automated quantification methods for orientational and translational order using shapelet functions, originally developed for analysis of images of galaxies, as a reduced-basis for surface pattern structure. In this work, a method combining shapelet functions and machine learning is developed and applied to a representative set of images of self-assembled surfaces from experimental characterization techniques including scanning electron miscroscopy, atomic force microscopy and transmission electron microscopy. The method is shown to be computationally efficient and able to quantify salient pattern features including deformation, defects, and grain boundaries from a broad range of patterns typical of self-assembly processes.

Formation and field-driven dynamics of nematic spheroids.

Unlike the canonical application of liquid crystals (LCs), LC displays, emerging technologies based on LC materials are increasingly leveraging the presence of nanoscale defects. The inherent nanoscale characteristics of LC defects present both significant opportunities as well as barriers for the application of this fascinating class of materials. Simulation-based approaches to the study of the effects of confinement and interface anchoring conditions on LC domains has resulted in significant progress over the past decade, where simulations are now able to access experimentally-relevant length scales while simultaneously capturing nanoscale defect structures. In this work, continuum simulations were performed in order to study the dynamics of micron-scale nematic LC spheroids of varying shape. Nematic spheroids are one of the simplest inherently defect-containing LC structures and are relevant to polymer-dispersed LC-based "smart" window technology. Simulation results include nematic phase formation and external field-switching dynamics of nematic spheroids ranging in shape from oblate to prolate. Results include both qualitative and quantitative insight into the complex coupling of nanoscale defect dynamics and structure transitions to micron-scale reorientation. Dynamic mechanisms are presented and related to structural transitions in LC defects present in the nematic domain. Domain-averaged metrics including order parameters and response times are determined for a range of experimentally-accessible electric field strengths. These results have both fundamental and technological relevance, in that increased understanding of LC dynamics in the presence of defects is a key barrier to continued advancement in the field.

Dynamics of ethyl cellulose nanoparticle self-assembly at the interface of a nematic liquid crystal droplet.

Design and fabrication of many next-generation liquid crystal (LC)-based devices rely on nematic LC domains in the form of drops or emulsions. In addition to surfactants, solid nanoparticles may be used to stabilize LC-in-water Pickering emulsions, possibly adding new dimensions to device functionality. In this work we quantitatively study the adsorption of ethyl cellulose (EC) nanoparticles, as a colloid model system, on the 4-cyano-4'-pentylbiphenyl (5CB)-water interface via a series of dynamic interfacial tension measurements. It is found that the planar alignment of 5CB molecules at the interface with water is unaffected by particle adsorption, but a significant reduction of the interfacial tension over time occurs. It is also found that adsorption of EC nanoparticles to the LC-water interface is irreversible and results in close hexagonal packing. This study demonstrates a systematic approach to quantitatively investigate the effect of nanoparticles on the stabilization of LC emulsions.

Automated quantification of one-dimensional nanostructure alignment on surfaces.

A method for automated quantification of the alignment of one-dimensional (1D) nanostructures from microscopy imaging is presented. Nanostructure alignment metrics are formulated and shown to be able to rigorously quantify the orientational order of nanostructures within a two-dimensional domain (surface). A complementary image processing method is also presented which enables robust processing of microscopy images where overlapping nanostructures might be present. Scanning electron microscopy (SEM) images of nanowire-covered surfaces are analyzed using the presented methods and it is shown that past single parameter alignment metrics are insufficient for highly aligned domains. Through the use of multiple parameter alignment metrics, automated quantitative analysis of SEM images is shown to be possible and the alignment characteristics of different samples are able to be quantitatively compared using a similarity metric. The results of this work provide researchers in nanoscience and nanotechnology with a rigorous method for the determination of structure/property relationships, where alignment of 1D nanostructures is significant.

Simple assembly of long nanowires through substrate stretching.

Although nanowire (NW) alignment has been previously investigated, minimizing limitations such as process complexity and NW breakage, as well as quantifying the quality of alignment, have not been sufficiently addressed. A simple, low cost, large-area, and versatile alignment method is reported that is applicable for NWs either grown on a substrate or synthesized in solution. Metal and semiconductor NWs with average lengths of up to 16 µm are aligned through the stretching of polyvinyl alcohol (PVA) films, which compared to other stretching methods results in superior alignment because of the large stretching ratio of PVA. Poly[oxy(methyl-1,2-ethanediyl)] is employed as lubricant to prevent NW breakage. To quantify NW alignment, a simple and effective image processing method is presented. The alignment process results in an order parameter (S) of NW alignment as high as 0.97.

Numerical Investigation of Shell-Side Flow Behavior and Vapor Distribution in Waste Heat Boilers.

Shell-and-tube waste heat boilers (STWHBs) are essential in the recovery of waste heat from high-temperature industrial processes. Kettle-type STWHBs are known to experience failures due to hold-up of steam, a significant concern in the industry. Multiphase computational fluid dynamics (CFD) simulations are used to study the effect of tube layout on the steam hold-up of an industrial-scale STWHB. Different design specifications are simulated including tube layout, heat flux, and pitch to predict steam hold-up performance and analyze thermo-hydrodynamic phenomena within the tube bundle. Simulation results show that, for similar tube bundle shape and size, 45° rotated square tube bundle layouts perform better, with respect to steam hold-up, than the square and triangle layouts for a range of heat flux duties. It is found that steam hold-up increases linearly with increasing heat flux and decreasing tube pitch, for the conditions simulated. The turbulent kinetic energy of the bubbly flow is greatly influenced by increasing phase fraction. Visualizations of the flow of water and steam within and around the tube bundle show that there is a vertical flow deviation for both staggered tube patterns (rotated square and triangle). These results motivate further multiphase CFD-based study of the thermo-hydrodynamics of STWHBs for improved understanding, retrofit, and new designs.

Diffuse-Interface Blended Method for Imposing Physical Boundaries in Two-Fluid Flows.

Multiphase flows are commonly found in chemical engineering processes such as distillation columns, bubble columns, fluidized beds and heat exchangers. The physical boundaries of domains in numerical simulations of multiphase flows are generally defined by a conformal unstructured mesh which, depending on the complexity of the physical system, results in time-consuming mesh generation which frequently requires user-intervention. Furthermore, the resulting conformal unstructured mesh could potentially contain a large number of skewed elements, which is undesirable for numerical stability and accuracy. The diffuse-interface approach allows for the use of a simple structured meshes to be used while still capturing the desired physical (e.g., solid-fluid) boundaries. In this work, a novel diffuse-interface method for the imposition of physical boundaries is developed for the incompressible two-fluid multiphase flow model. This model is appropriate for dispersed multiphase flows which are pervasive in chemical engineering processes, in that this flow regime results in high levels of mass and energy transfer between phases. A diffuse interface is used to define the physical boundaries and boundary conditions are imposed by blending the conservation equations from the two-fluid model with that of the nondeformable solid. The results from the diffuse-interface method are compared with results from a conformal unstructured mesh for different interface functions and widths. For small interface widths, the accuracy of the flow profile is unaffected by the choice of interface function and the phase fraction distribution and flow behavior are within 3% compared to those from a conformal mesh. As the interface width increases, the diffuse-interface solution deviates from the conformal mesh solution in both the localized gas fraction and the overall gas hold-up, resulting in a difference up to 30%. In the case of flow past a cylinder, where the solid interacts with the flow, the presence of the diffuse interface extends the thickness of the solid boundary and results in a deviation from the conformal mesh solution as time increases.

Theory and computation of directional nematic phase ordering.

A computational study of morphological instabilities of a two-dimensional nematic front under directional growth was performed using a Landau-de Gennes-type quadrupolar tensor order parameter model for the first-order isotropic-nematic transition of 5CB (pentyl-cyanobiphenyl). A previously derived energy balance, taking anisotropy into account, was utilized to account for latent heat and an imposed morphological gradient in the time-dependent model. Simulations were performed using an initially homeotropic isotropic-nematic interface. Thermal instabilities in both the linear and nonlinear regimes were observed and compared to past experimental and theoretical observations. A sharp-interface model for the study of linear morphological instabilities, taking into account additional complexity resulting from liquid-crystalline order, was derived. Results from the sharp-interface model were compared to those from full two-dimensional simulation identifying the specific limitations of simplified sharp-interface models for this liquid-crystal system. In the nonlinear regime, secondary instabilities were observed to result in the formation of defects, interfacial heterogeneities, and bulk texture dynamics.

A Topologically-Informed Hyperstreamline Seeding Method for Alignment Tensor Fields.

A topologically-informed hyperstreamline seeding method is presented for visualization of alignment tensor fields. The method is inspired by and applied to visualization of nematic liquid crystal (LC) orientation dynamics simulations. The method distributes hyperstreamlines along domain boundaries and edges of a nearest-neighbor graph whose vertices are degenerate regions of the alignment tensor field, which correspond to orientational defects in a nematic LC domain. This is accomplished without iteration while conforming to a user-specified spacing between hyperstreamlines and avoids possible failure modes associated with hyperstreamline integration in the vicinity of degeneracies in alignment (orientational defects). It is shown that the presented seeding method enables automated hyperstreamline-based visualization of a broad range of alignment tensor fields which enhances the ability of researchers to interpret these fields and provides an alternative to using glyph-based techniques.

Field-driven dynamics of nematic microcapillaries.

Polymer-dispersed liquid-crystal (PDLC) composites long have been a focus of study for their unique electro-optical properties which have resulted in various applications such as switchable (transparent or translucent) windows. These composites are manufactured using desirable "bottom-up" techniques, such as phase separation of a liquid-crystal-polymer mixture, which enable production of PDLC films at very large scales. LC domains within PDLCs are typically spheroidal, as opposed to rectangular for an LCD panel, and thus exhibit substantially different behavior in the presence of an external field. The fundamental difference between spheroidal and rectangular nematic domains is that the former results in the presence of nanoscale orientational defects in LC order while the latter does not. Progress in the development and optimization of PDLC electro-optical properties has progressed at a relatively slow pace due to this increased complexity. In this work, continuum simulations are performed in order to capture the complex formation and electric field-driven switching dynamics of approximations of PDLC domains. Using a simplified elliptic cylinder (microcapillary) geometry as an approximation of spheroidal PDLC domains, the effects of geometry (aspect ratio), surface anchoring, and external field strength are studied through the use of the Landau-de Gennes model of the nematic LC phase.

Theory and application of shapelets to the analysis of surface self-assembly imaging.

A method for quantitative analysis of local pattern strength and defects in surface self-assembly imaging is presented and applied to images of stripe and hexagonal ordered domains. The presented method uses "shapelet" functions which were originally developed for quantitative analysis of images of galaxies (∝10(20)m). In this work, they are used instead to quantify the presence of translational order in surface self-assembled films (∝10(-9)m) through reformulation into "steerable" filters. The resulting method is computationally efficient (with respect to the number of filter evaluations), robust to variation in pattern feature shape, and, unlike previous approaches, is applicable to a wide variety of pattern types. An application of the method is presented which uses a nearest-neighbor analysis to distinguish between uniform (defect-free) and nonuniform (strained, defect-containing) regions within imaged self-assembled domains, both with striped and hexagonal patterns.

Nanoscale surface pattern evolution in heteroepitaxial bimetallic films.

Nanoscale self-assembly dynamics of submonolayer bimetallic films was studied through simulation of a coarse-grained mesoscopic model. Simulations predict a phase transition sequence (hexagonal→stripe→inverse hexagonal) consistent with experimental observations of Pb/Cu(111) heteroepitaxial growth. Post-transition ordering dynamics of hexagonal and inverse hexagonal patterns was simulated and quantified in order to predict pattern quality and evolution mechanisms. Correlation length scaling laws and nanoscale evolution mechanisms were predicted through simulation of experimentally relevant length (≈1 µm(2)) and time scales, with findings supporting evidence of universal pattern behavior with other hexagonal systems. Results provide detailed dynamics and structure of this novel self-assembly process applicable to the design and optimization of functional bimetallic materials, such as bimetallic catalysts.

Nonisothermal model for the direct isotropic/smectic-A liquid-crystalline transition.

An extension to a high-order model for the direct isotropic/smectic-A liquid-crystalline phase transition was derived to take into account thermal effects including anisotropic thermal diffusion and latent heat of phase ordering. Multiscale multitransport simulations of the nonisothermal model were compared to isothermal simulation, showing that the presented model extension corrects the standard Landau-de Gennes prediction from constant growth to diffusion-limited growth under shallow quench/undercooling conditions. Nonisothermal simulations, where metastable nematic preordering precedes smectic-A growth, were also conducted, and novel nonmonotonic phase-transformation kinetics were observed.

Non-isothermal model for nematic spherulite growth.

A computational study of the growth of two-dimensional nematic spherulites in an isotropic phase was performed using a Landau-de Gennes-type quadrupolar tensor order parameter model for the first-order isotropic/nematic transition of 5CB (pentylcyanobiphenyl). An energy balance, taking anisotropy into account, was derived and incorporated into the time-dependent model. Growth laws were determined for two different spherulite morphologies of the form t(n), with and without the inclusion of thermal effects. Results show that incorporation of the thermal energy balance correctly predicts the transition of the growth law exponent from the volume driven regime (n=1) to the thermally limited regime (approaching n = 1/2), agreeing well with experimental observations. An interfacial nematodynamic model is used to gain insight into the interactions that result in the progression of different spherulite growth regimes.