Macroscale Structures Research Articles

Control over Structure and Properties in Nanocrystal Aerogels at the Nano-, Micro-, and Macroscale

ConspectusThe assembly of individual colloidal nanocrystals into macroscopic solvogels and aerogels introduced a new exciting type of material into the class of porous architectures. In these so-called nanocrystal gels, the structure and properties can be controlled and fine-tuned to the smallest details. Recently it was shown that by employing nanocrystal building blocks for such gel materials, the interesting nanoscopic properties can be conserved or even expanded to properties that are available neither in the nanocrystals nor in their respective bulk materials. In general, the production of these materials features the wet-chemical synthesis of stable nanocrystal colloids followed by their carefully controlled destabilization to facilitate arrangement of the nanocrystals into highly porous, interconnected networks. By isolation of the synthesis of the discrete building blocks from the assembly process, the electronic structure, optical properties, and structural morphology can be tailored by the myriad of procedures developed in colloidal nanocrystal chemistry. Furthermore, knowledge and control over the structure–property correlation in the resulting gel structures opens up numerous new ways for extended and advanced applications. Consequently, the amount of different materials converted to nanocrystal-based gel structures is rising steadily. Meanwhile the number of methods for assembly initiation is likewise increasing, offering control over the overall network structure and porosity as well as the individual nanocrystal building block connection. The resulting networks can be dried by different methods to obtain highly porous air-filled networks (aerogels) or applied in their wet form (solvogels). By now a number of different applications profiting from the unique advantages of nanocrystal-based gel materials have been realized and exploited in the areas of photocatalysis, electrocatalysis, and sensing.In this Account, we aim to summarize the efforts undertaken in the structuring of nanocrystal-based network materials on different scales, fine-tuning of the individual building blocks on the nanoscale, the network connections on the microscale, and the macroscale structure and shape of the final construct. It is exemplarily demonstrated how cation exchange reactions (at the nanoscale), postgelation modifications on the nanocrystal networks (microscale), and the structuring of the gels via printing techniques (macroscale) endow the resulting nanocrystal gel networks with novel physicochemical, mechanical, and electrocatalytic properties. The methods applied in the more traditional sol–gel chemistry targeting micro- and macroscale structuring are also reviewed, showing their future potential promoting the field of nanocrystal-based aerogels and their applications.

An improved multi-scale two phase method for bubbly flows

Multiple spatial scale is an important characteristic of two phase flow phenomena. The micro-scale and macro-scale flow structures are obviously different in flow state and have different effects on the mass, momentum and energy transfer between two phases. Different modeling approaches have been developed for each scale physical phenomenon in traditional numerical simulations. However, it is difficult to simulate two phase flow systems with multi-scale flow structures simultaneously. In order to address this problem, a multi-scale two phase method is developed based on the combination of Volume of Fluid (VOF) interface capture method and Euler–Lagrange particle tracking method. The fundamental assumption of the present method is that there is a clear scale separation between VOF interfaces and bubbles. Therefore, VOF method with artificial compressive algorithm is used to simulate the dynamic evolution of macro-scale air-water interface. While Euler–Lagrange method is used to track the micro-scale bubbles that cannot be captured in grids. Collision, coalescence and breakup of Lagrange bubbles and two-way coupling are fully considered to construct a comprehensive micro-bubble solving procedure. Transformation criteria and the corresponding algorithms between micro-scale and macro-scale flow structures are designed and discussed in detail. In addition, a new curvature-based algorithm for the transformation from VOF interface to Lagrange bubbles is proposed. Simulations of typical two phase flow problems involving multi-scale flow transformation are carried out to test the performance of the multi-scale solver. Results indicate that the multi-scale two phase method performs significantly better than the pure VOF method in capturing micro-scale phenomena. Besides, the curvature-based transformation algorithm proposed in this paper is proved to be more precise and efficient than the previous identify-based one. From the perspective of simulation accuracy and efficiency, the multi-scale two phase method is more promising for the simulation of actual complex two-phase flows.

Comparison of the mechanical performance of architected three-dimensional intertwined lattices at the macro/microscale

The design of lattice structures with exceptional mechanical performance has been accentuated by recent advances in both additive manufacturing and mechanical modeling. Although there is a plethora of different lattice structures with intriguing properties, such as auxeticity and reciprocity, an exceptional class of lattice geometries is that of intertwined lattices, designed by the tactical coalition of polyhedral structures. Although the superior mechanical performance of the latter structures has been demonstrated at the microscale, their mechanical analysis is still incipient. In this study, the design principles and mechanical performance of such three-dimensional structures were examined at the macroscale and juxtaposed with their microscale counterparts. As a proof of concept, the first stellation of the rhombic dodecahedron, an ultralight/ultrastiff architected structure with superior stiffness and strain hardening characteristics, was examined both numerically and experimentally. Finite element analysis showed that intertwining greatly enhances both the stiffness and isotropic behavior of the structure. In addition, mechanical testing of both microscale and macroscale structures revealed that lattice intertwining leads to commensurate stiffness and strain energy density compared to that of the bulk material, even for 20% relative density. The findings of this study pave the way for a systematic and rigorous approach to design and modeling of macroscopic intertwined geometries, for comparing them with their microscopic equivalents, and for providing insight into scale effects on the mechanical performance of architected materials with intertwined lattices.

Breaking Droplet Jumping Energy Conversion Limits with Superhydrophobic Microgrooves.

Coalescence-induced droplet jumping has the potential to enhance the performance of a variety of applications including condensation heat transfer, surface self-cleaning, anti-icing, and defrosting to name a few. Here, we study droplet jumping on hierarchical microgrooved and nanostructured smooth superhydrophobic surfaces. We show that the confined microgroove structures play a key role in tailoring droplet coalescence hydrodynamics, which in turn affects the droplet jumping velocity and energy conversion efficiency. We observed self-jumping of individual deformed droplets within microgrooves having maximum surface-to-kinetic energy conversion efficiency of 8%. Furthermore, various coalescence-induced jumping modes were observed on the hierarchical microgrooved superhydrophobic surface. The microgroove structure enabled high droplet jumping velocity (≈0.74U) and energy conversion efficiency (≈46%) by enabling the coalescence of deformed droplets in microgrooves with undeformed droplets on adjacent plateaus. The jumping velocity and energy conversion efficiency enhancements are 1.93× and 6.67× higher than traditional coalescence-induced droplet jumping on smooth superhydrophobic surfaces. This work not only demonstrates high droplet jumping velocity and energy conversion efficiency but also demonstrates the key role played by macroscale structures on coalescence hydrodynamics and elucidates a method to further control droplet jumping physics for a plethora of applications.

Titanium Dioxide Microscale and Macroscale Structures: A Mini-Review.

Titanium dioxide nanoparticles (TiO2 NPs) have some limitations, such as their low surface area, high bandgap energy, and low recycling ability. To overcome these limitations, TiO2 can be prepared in microscale/macroscale structures. TiO2 microscale structures, in comparison with TiO2 nanopowder, have higher surface areas, more tunable pore structures, and better top photocatalytic activity. In contrast, for TiO2 macroscale structures, although the surface area is lower than TiO2 nanopowder in many cases, they still achieve similar or better photocatalytic performance due to their unique properties. Moreover, both TiO2 microscale and macroscale structures can be easily recovered from reaction media. The difference between these two types of TiO2 structures is a function not only of size but also of the preparation process. Every type of TiO2 structure has its own advantages and disadvantages, as will be discussed further in the following pages. Future perspectives on this research field also will be discussed.

Molecular Modeling and Simulations of Peptide-Polymer Conjugates.

Peptide-polymer conjugates are a class of soft materials composed of covalently linked blocks of protein/polypeptides and synthetic/natural polymers. These materials are practically useful in biological applications, such as drug delivery, DNA/gene delivery, and antimicrobial coatings, as well as nonbiological applications, such as electronics, separations, optics, and sensing. Given their broad applicability, there is motivation to understand the molecular and macroscale structure, dynamics, and thermodynamic behavior exhibited by such materials. We focus on the past and ongoing molecular simulation studies aimed at obtaining such fundamental understanding and predicting molecular design rules for the target function. We describe briefly the experimental work in this field that validates or motivates these computational studies. We also describe the various models (e.g., atomistic, coarse-grained, or hybrid) and simulation methods (e.g., stochastic versus deterministic, enhanced sampling) that have been used and the types of questions that have been answered using these computational approaches.

Design and preparation of icephobic PDMS-based coatings by introducing an aqueous lubricating layer and macro-crack initiators at the ice-substrate interface

Preventing ice accretion on exposed surfaces is important to the operational performance of various facilities and devices. As time elapses and temperature lowers sufficiently, ice accretion becomes inevitable. Herein, we present a new approach to prepare icephobic coatings by incorporating two strategies towards lowering ice adhesion strength, i.e. introducing an aqueous lubricating layer and maximizing macro-crack initiators at the ice-substrate interface. The aqueous lubricating layer is realized by grafting poly(acrylic acid) (PAA) onto polydimethylsiloxane (PDMS) coatings, and the macro-crack initiators are induced by introducing macro-scale hollow sub-surface structures into PDMS coatings. By using vertical shear tests, ice adhesion strengths of PAA-g-PDMS (10:1), PDMS coatings with macro-scale hollow sub-surface structures (hPDMS) (10:1), PAA-g-hPDMS (10:1), PAA-g-PDMS (10:10), hPDMS (10:10), and PAA-g-hPDMS (10:10) coatings are obtained as 178.5 ± 22 kPa, 153.1 ± 19 kPa, 122.7 ± 18 kPa, 24.6 ± 4 kPa, 20.3 ± 3.4 kPa and 17.6 ± 3.2 kPa, respectively, showing a reduction of 37.2 %, 46.1 %, 56.8 %, 32.8 %, 44.5 % and 51.9 % when compared with corresponding pure PDMS coatings. These results indicate that ice adhesion strength can be further reduced by simultaneously introducing two strategies. The principle of designing icephobic coatings by combining two or more strategies to reduce ice adhesion to as low as possible provides a new avenue to the preparation of icephobic coatings, and makes practical applications possible under extremely severe conditions.

Additive Manufacturing of Carbon Nanotube-Based Three-Dimensional Multi-Scale Architectures

Carbon nanotubes (CNT) have exceptional properties, but there is no effect to assemble CNT into macro-scale structures with desired architecture. Three-dimensional CNT-based multiscale architecture featuring the characteristics of both the constituent CNT material, which brings the effects of its nanoscale resolution and properties, as well as the structures across multiscale lengths offer breakthrough advances in many applications including ultra-light structural materials, energy storage, and biomedical devices. In my talk, I will introduce our recent work on additive manufacturing of three-dimensional CNT-based multiscale architectures, and demonstrate its potential application in battery application, including Li anode protection and solid state composite electrolyte.

Efficient multiscale modeling for woven composites based on self-consistent clustering analysis

Multiscale simulation of woven composites structure remains a challenge due to extremely expensive computational cost for solving the nonlinear woven Representative Volume Element (RVE). Recently, an effective and efficient Reduced Order modeling method, namely Self-consistent Clustering Analysis (SCA), is proposed to solve the RVE problem. In this work, the curse of computational cost in woven RVE problem is countered using the SCA, which maintains a considerable accuracy compared with the standard Finite Element Method (FEM). The Hill anisotropic yield surface is predicted efficiently using the woven SCA, which can accelerate the microstructure optimization and design of woven composites. Moreover, a two-scale FEM×SCA modeling framework is proposed for woven composites structure. Based on this framework, the complex behavior of the composite structures in macroscale can be predicted using microscale properties. Additionally, macroscale and mesoscale physical fields are captured simultaneously, which are hard, if not impossible, to observe using experimental methods. This will expedite the deformation mechanism investigation of composites. A numerical study is carried out for T-shaped hooking structures under cycle loading to illustrate these advantages.

A hybrid density/level set formulation for topology optimization of functionally graded lattice structures

Additive manufacturing is capable of producing lightweight structures by introducing mesoscale lattice structures in the design without significant additional manufacturing costs. Nevertheless, designing efficient structures including complex lattices remains a challenging task. This paper presents a strategy for the design of additively manufactured structures that is able to simultaneously optimize the shape of the macroscale structure and the functionally graded lattices inside this design. Assuming a separation of scales between the lattice cell size and the macroscale structure, an effective material model based on numerical homogenization is adopted to model the lattice behavior in the analysis of the macroscale structure. While this material model is parametrized by volume densities to mimic functionally graded lattices, the shape of the macroscale structure is represented by a level set function and modeled by the extended finite element method inside the design domain. By adopting an explicit approach to the level set optimization the design problem can be formulated as a single nonlinear programming problem which can be solved with standard optimization algorithms for topology optimization. The proposed formulation avoids degenerate lattice members by excluding small densities in the optimization. Furthermore, the distinct representation of the macroscale structure enables to easily include geometric constraints on the macroscale level such as a minimum feature size or other constraints specific to the additive manufacturing process. The effectiveness of the method is demonstrated in a number of examples.

High-speed in vitro intensity diffraction tomography

We demonstrate a label-free, scan-free {\it intensity} diffraction tomography technique utilizing annular illumination (aIDT) to rapidly characterize large-volume 3D refractive index distributions in vitro. By optimally matching the illumination geometry to the microscope pupil, our technique reduces the data requirement by 60$\times$ to achieve high-speed 10 Hz volume rates. Using 8 intensity images, we recover $\sim350\times100\times20\mu$m$^3$ volumes with near diffraction-limited lateral resolution of 487 nm and axial resolution of 3.4 $\mu$m. Our technique's large volume rate and high resolution enables 3D quantitative phase imaging of complex living biological samples across multiple length scales. We demonstrate aIDT's capabilities on unicellular diatom microalgae, epithelial buccal cell clusters with native bacteria, and live \emph{Caenorhabditis elegans} specimens. Within these samples, we recover macro-scale cellular structures, subcellular organelles, and dynamic micro-organism tissues with minimal motion artifacts. Quantifying such features has significant utility in oncology, immunology, and cellular pathophysiology, where these morphological features are evaluated for changes in the presence of disease, parasites, and new drug treatments. Finally, we simulate our aIDT system to highlight the accuracy and sensitivity of our technique. aIDT shows promise as a powerful high-speed, label-free computational microscopy technique applications where natural imaging is required to evaluate environmental effects on a sample in real-time. We provide example datasets and an open source implementation of aIDT at \href{https://github.com/bu-cisl/IDT-using-Annular-Illumination}{https://github.com/bu-cisl/IDT-using-Annular-Illumination}.

Mechanochemical Adhesion and Plasticity in Multifiber Hydrogel Networks.

The extracellular matrix (ECM) has force-responsive (i.e., mechanochemical) properties that enable adaptation to mechanical loading through changes in fibrous network structure and interfiber bonding. Imparting such properties into synthetic fibrous materials will allow reinforcement under mechanical load, the potential for material self-adhesion, and the general mimicking of ECM. Multifiber hydrogel networks are developed through the electrospinning of multiple fibrous hydrogel populations, where fibers contain complementary chemical moieties (e.g., aldehyde and hydrazide groups) that form covalent bonds within minutes when brought into contact under mechanical load. These fiber interactions lead to microscale anisotropy, as well as increased material stiffness and plastic deformation. Macroscale structures (e.g., tubes and layered scaffolds) are fabricated from these materials through interfiber bonding and adhesion when placed into contact while maintaining a microscale fibrous architecture. The design principles for engineering plasticity described can be applied to numerous material systems to introduce unique properties, from textiles to biomedical applications.

Numerical simulation of a drop impact on a superhydrophobic surface with a wire

Superhydrophobic surfaces patterned with macroscale (≈1 mm) structures have gained increasing interest in the past years because of their potential in reducing the contact time between impacting liquid drops and the solid surface. The reduced wettability of these surfaces is of interest in numerous technical applications, as, for example, in anti-icing on airplane wings. Several experimental studies have been carried out on this topic in the literature; on the other hand, only very limited numerical investigations are available in the literature. In this paper, we present a numerical study based on a volume of fluid code for direct numerical simulation of incompressible multiphase flows. A necessary condition for the realization of this study was the implementation of arbitrary-shaped boundaries using a Cartesian grid system. Our implementation of embedded boundaries is based on a volume fraction representation of the boundaries and on a piecewise linear approximation of their surface. The discretized boundaries are then cut off from the computational domain, leading to an altered formulation of the discretized governing equations. To validate the method, we show simulation results for different impact velocities for the case of a droplet impacting on a wire, which has been investigated experimentally in the literature. The simulations show good agreement in terms of contact time and impact morphology, thus, showing the validity of the implementation. Moreover, an extensive analysis of the velocity field for this setup is presented, helping us to better understand the underlying physical phenomena.

Micromorphological evidence for the role of pressurised water in the formation of large-scale thrust-block moraines in Melasveit, western Iceland

AbstractPressurised meltwater has a major impact on ice dynamics, as well as on sedimentary and deformational processes occurring below/in front of glaciers and ice sheets, but its role in glaciotectonic processes is yet to be fully understood. This study explores micro- and macroscale structures developed within décollements in two thrust-block moraines of Late Weichselian age in Melasveit, western Iceland. The aim is to investigate how pressurised subglacial meltwater can aid the dislocation and transport of large, unfrozen and unlithified sediment blocks by glaciers. A detailed model is constructed for the development of the thrust-block moraines and the microscale processes occurring along their detachments during thrusting. The detachments are characterized by relatively thin zones of crosscutting hydrofractures, which reflect fluctuating water pressures during glaciotectonism. Little evidence of shearing is observed along the leading edges of the thrusts in both moraines. This is supported by high water pressures along the detachments and indicates that the thrust blocks were initially decoupled from the underlying deposits. As the thrust moraines evolved, an increased amount of shear occurred in between events of sediment liquefaction, hydrofracturing, and fluid escape. This was followed by progressive locking up of the detachments and eventual cessation in the accretion of the thrust blocks.

Multiscale design for additive manufactured structures with solid coating and periodic infill pattern

This paper considers multiscale topology optimization of an infill structure. The structure is composed of an optimized layout configuration at the macroscale with uniform optimized microstructures as infill lattices coated by a thin skin. The design optimization of the infill lattice is performed simultaneously with the topology optimization of macroscale structure, which also includes the coating. The classic Solid Isotropic Material with Penalization (SIMP) method is used to design the topology of the microstructure. The Novel Implementation of Asymptotic Homogenization (NIAH) evaluates the effective properties of the microstructure; the macroscale structural analysis uses these homogenized properties. The Porous Anisotropic Material with Penalization (PAMP) method realizes the two-scale topology optimization of the macrostructure and microstructure. Harmonic-mean based non-linear filters identify the coating layer and realize length scale control on the topologies of the macrostructure as well as the microstructure. These morphology mimicking non-linear filters also distinguish the skin and the infill lattice parts of the design at the macroscale. Several numerical examples demonstrate the effectiveness of the proposed optimization method.

Strong vorticity fluctuations and antiferromagnetic correlations in axisymmetric fluid equilibria

The macroscale structure and microscale fluctuation statistics of late-time asymptotic steady state flows in cylindrical geometries is studied using the methods of equilibrium statistical mechanics. The axisymmetric assumption permits an effective two-dimensional description in terms of the (toroidal) flow field $\sigma$ about the cylinder axis and the vorticity field $\xi$ that generates mixing within the (poloidal) planes of fixed azimuth. As for a number of other 2D fluid systems, extending the classic 2D Euler equation, the flow is constrained by an infinite number of conservation laws, beyond the usual kinetic energy and angular momentum. All must be accounted for in a consistent equilibrium description. It is shown that the most directly observable impact of the conservation laws is on $\sigma$, which displays interesting large-scale radius-dependent flow structure. However, unlike in some previous treatments, we find that the thermodynamic temperature is always positive. As a consequence, except for an infinitesimal boundary layer that maintains the correct (conserved) value of the overall poloidal circulation, the impact on $\xi$ resides in the statistics of the strongly fluctuating, fine-scale mixing, where it is sensitive to `antiferromagnetic' microscale correlations that help maintain the analogue of local charge neutrality. The poloidal flow is macroscopically featureless, displaying no large scale circulating jet- or eddy-like features (which typically emerge as negative temperature states in analogous Euler and quasigeostrophic equilibria).

Spatial distribution of nanodiamond and its effect on mechanical behaviour of epoxy based composite using 2D modulus mapping

The present study has taken an initiative to understand the distribution of nanophase reinforcement in polymer matrix and their behaviour during loading, using 2D modulus mapping. The composite system, being studied here, is a nanodiamond reinforced epoxy resin matrix. Modulus Mapping gives an idea of distribution of nanodiamond in matrix, in terms of spatial distribution of micron level higher modulus regions in epoxy matrix. The modulus mapping studies, carried out on composites with and without application of uniaxial tensile stresses, reveals the active role being played by nanodiamond in modulating the mechanical behaviour of the epoxy matrix and the evolution of distribution of the former with application of stress. Hardness and elastic modulus of epoxy is improved by ∼470% and ∼94% with 1 wt% nanodiamond. The stiffening effect of nanodiamond dispersed in epoxy matrix, evaluated through experiment is also in concurrence with results simulated using finite element method (FEM) of the representative volume element (RVE). Tensile strength and fracture toughness also showed an improvement of ∼56% and ∼85%, respectively, with 0.3 wt% ND. Interestingly, % strain (at break) also increased by ∼66%. TEM showed good dispersion and strong interaction of NDs with epoxy matrix. SEM analysis validates crack pinning and crack deflection as dominant toughening mechanism, while, efficient load sharing between ND and epoxy is found as main strengthening mechanism. As a whole, this study develops 2D modulus mapping technique as a generalized tool for evaluating the quality of dispersion of the nanoscale reinforcement phases and their role in mechanical behaviour of the macro-scale composite structures.

Self-aligned and hierarchically porous graphene-polyurethane foams for acoustic wave absorption

Manipulating the morphology of three-dimensional (3D) cellular structures in both macroscale and microscale is very important in designing a sound absorbing material effective in a broad frequency bandwidth. However, it is extremely difficult to synthesize the hierarchical porous structures having nano- and micro-pores in a self-assembled or controlled manner. Herein, we report an efficient strategy to fabricate the self-aligned and hierarchically porous graphene-polyurethane foams as a sound absorbing material via electrostatic repulsion mechanism of graphene oxide and potassium hydroxide activation. Two unique microscopic cellular structures are designed by controlling the morphology of graphene layers inside the polyurethane backbone using spontaneous self-alignment and stochastic disruptive methods, respectively. The obtained heterogeneous graphene microstructure network provides enhanced mechanically load-bearing ability and significantly improves the sound energy attenuation performance over 312% compared to pristine sound absorber depending on the existence of ordered or disordered graphene lattices, resulting in an efficient pathway for rapidly decaying out acoustic wave energy.

Rapid assembling organ prototypes with controllable cell-laden multi-scale sheets

A native organ has heterogeneous structures, strength, and cell components. It is a big challenge to fabricate organ prototypes with controllable shapes, strength, and cells. Herein, a hybrid method is developed to fabricate organ prototypes with controlled cell deposition by integrating extrusion-based 3D printing, electrospinning, and 3D bioprinting. Multi-scale sheets were first fabricated by 3D printing and electrospinning; then, all the sheets were assembled into organ prototypes by sol–gel reaction during bioprinting. With this method, macroscale structures fabricated by 3D printing ensure the customized structures and provide mechanical support, nanoscale structures fabricated by electrospinning offer a favorable environment for cell growth, and different types of cells with controllable densities are deposited in accurate locations by bioprinting. The results show that L929 mouse fibroblasts encapsulated in the structures exhibited over 90% survival within 10 days and maintained a high proliferation rate. Furthermore, the cells grew in spherical shapes first and then migrated to the nanoscale fibers showing stretched morphology. Additionally, a branched vascular structure was successfully fabricated using the presented method. Compared with other methods, this strategy offers an easy way to simultaneously realize the shape control, nanofibrous structures, and cell accurate deposition, which will have potential applications in tissue engineering.

Differential construction response to humidity by related species of mound-building termites.

Macrotermes michaelseni and M. natalensis are two morphologically similar termite species occupying the same habitat across southern Africa. Both build large mounds and tend mutualistic fungal symbionts for nutrients, but despite these behavioural and physiological similarities, the mound superstructures they create differ markedly. The behavioural differences behind this discrepancy remain elusive, and are the subject of ongoing investigations. Here, we show that the two species demonstrate distinctive building activity in a laboratory-controlled environment consisting of still air with low ambient humidity. In these conditions, M. michaelseni transports less soil from a central reservoir, deposits this soil over a smaller area, and creates structures with a smaller volumetric envelope than M. natalensis In high humidity, no such systematic difference is observed. This result suggests a differential behavioural threshold or sensitivity to airborne moisture that may relate to the distinct macro-scale structures observed in the African bushland.