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At least 289 records · Page 16

Robust block preconditioners for poroelasticity

In this paper we develop and analyze several preconditioners for the linear systems arising from discretized poroelasticity problems. The preconditioners include one block preconditioner for the two-field Biot model and several preconditioners for the classical three-field Biot model. We manage to analyze these different preconditioners under a same theoretical framework and show that all of them are uniformly optimal with respect to material and discretization parameters. Numerical tests demonstrate the robustness of these preconditioners.

42 ENGINEERING↗

Potent transmission-blocking monoclonal antibodies from naturally exposed individuals target a conserved epitope on Plasmodium falciparum Pfs230

Pfs230 is essential for Plasmodium falciparum transmission to mosquitoes and is the protein targeted by the most advanced malaria-transmission-blocking vaccine candidate. Prior understanding of functional epitopes on Pfs230 is based on two monoclonal antibodies (mAbs) with moderate transmission-reducing activity (TRA), elicited from subunit immunization. Here, we screened the B cell repertoire of two naturally exposed individuals possessing serum TRA and identified five potent mAbs from sixteen Pfs230 domain-1-specific mAbs. Structures of three potent and three low-activity antibodies bound to Pfs230 domain 1 revealed four distinct epitopes. Highly potent mAbs from natural infection recognized a common conformational epitope that is highly conserved across P. falciparum field isolates, while antibodies with negligible TRA derived from natural infection or immunization recognized three distinct sites. Our study provides molecular blueprints describing P. falciparum TRA, informed by contrasting potent and non-functional epitopes elicited by natural exposure and vaccination.

60 APPLIED LIFE SCIENCES↗

Optimal design of chemoepitaxial guideposts for the directed self-assembly of block copolymer systems using an inexact Newton algorithm

Directed self-assembly (DSA) of block copolymers (BCPs) is one of the most promising developments in the cost-effective production of nanoscale devices. The process makes use of the natural tendency for BCP melts to form nanoscale structures upon phase separation. The phase separation can be directed through the use of chemically patterned substrates to promote the formation of morphologies that are essential to the production of semiconductor devices. Moreover, the design of substrate pattern can be formulated as an optimization problem for which we seek optimal substrate designs that effectively produce given target morphologies. In this paper, we adopt a phase field model given by a nonlocal Cahn–Hilliard partial differential equation (PDE) based on the minimization of the Ohta–Kawasaki free energy, and present an efficient PDE-constrained optimization framework for the optimal design problem. The design variables are the locations of circular- or strip-shaped guiding posts that are used to model the substrate chemical pattern. To solve the ensuing optimization problem, we propose a variant of an inexact Newton conjugate gradient algorithm tailored to this problem. Additionally, we demonstrate the effectiveness of our computational strategy on numerical examples that span a range of target morphologies. Owing to our second-order optimizer and fast state solver, the numerical results demonstrate five orders of magnitude reduction in computational cost over previous work. The efficiency of our framework and the fast convergence of our optimization algorithm enable us to rapidly solve the optimal design problem in not only two, but also three spatial dimensions.

97 MATHEMATICS AND COMPUTING↗

Large-Grained Cylindrical Block Copolymer Morphologies by One-Step Room-Temperature Casting

We report a facile method of ordering block copolymer (BCP) morphologies in which the conventional two-step casting and annealing steps are replaced by a single-step process where microphase separation and grain coarsening are seamlessly integrated within the casting protocol. This is achieved by slowing down solvent evaporation during casting by introducing a non-volatile solvent into the BCP casting solution what effectively prolongs the duration of the grain-growth phase. We demonstrate the utility of this solvent evaporation annealing (SEA) method by producing well-ordered large molecular-weight BCP thin films in a total processing time shorter than 3 minutes without resorting to any extra laboratory equipment other than a basic casting-device i.e., spin- or blade-coater. By analyzing the morphologies of the quenched samples, we identify a relatively narrow range of polymer concentration in the wet film, just above the order-disorder concentration, to be critical for obtaining large-grained morphologies. This finding is corroborated by the analysis of the grain-growth kinetics of horizontally-oriented cylindrical domains where relatively large growth exponents (1/2) are observed, indicative of a more rapid defect-annihilation mechanism in the concentrated BCP solution than in thermally-annealed BCP melts. Furthermore, the analysis of temperature-resolved kinetics data allows us to calculate the Arrhenius activation energy of the grain-coarsening in this one-step BCP ordering process.

36 MATERIALS SCIENCE↗

Ion Gating in Nanopore Electrode Arrays with Hierarchically Organized pH-Responsive Block Copolymer Membranes

Inspired by biological ion channels, artificial nanopore-based architectures have been developed for smart ion/molecular transport control with potential applications to iontronics and energy conversion. Advances in nanofabrication technology enable simple, versatile construction methods, and post-fabrication functionalization delivers nanochannels with unique ion transport-control attributes. Here, we characterize a pH-responsive, charge-selective dual-gating block copolymer (BCP) membrane composed of polystyrene-b-poly(4-vinylpyridine) (PS 48400 -b-P4VP 21300 ), capable of self-organizing into highly ordered nanocylindrical domains. Because the PS-b-P4VP membrane exhibits pH-dependent structural transitions, it is suitable for designing intelligent pH-gated biomimetic channels, for example, exhibiting on–off transport switching at pH values near the pK a of P4VP with excellent anion permselectivity at pH < pK a . Introducing the BCP membrane onto nanopore electrode arrays (BCP@NEAs) allows the BCP to serve as a pH-responsive gate controlling ion transfer into the NEA nanopores. Such selectively transported and confined ions are detected by using a 100 nm gap dual-ring nanoelectrode structure capable of enhancing current output by efficient redox cycling with an amplification factor >10 2 . In addition, BCP@NEAs exhibit extraordinary pH-gated ion selectivity, resulting in a 3380-fold current difference between anion and cation probes at pH 3.0. Furthermore, this hierarchically organized BCP-gated NEA system can serve as a template for the development of other stimulus-responsive ion gates, for example, those based on temperature and ligand gating, thus exploiting the intrinsic advantages of NEAs, such as enhanced sensitivity based on redox cycling, which may lead to technological applications such as engineered biosensors and iontronic devices.

36 MATERIALS SCIENCE↗

Zincate-Blocking-Functionalized Polysulfone Separators for Secondary Zn–MnO 2 Batteries

Alkaline zinc–manganese dioxide (Zn–MnO 2 ) batteries are well suited for grid storage applications because of their inherently safe, aqueous electrolyte and established materials supply chain, resulting in low production costs. With recent advances in the development of Cu/Bi-stabilized birnessite cathodes capable of the full 2-electron capacity equivalent of MnO 2 (617 mA h/g), there is a need for selective separators that prevent zincate (Zn(OH) 4 ) 2– transport from the anode to the cathode during cycling, as this electrode system fails in the presence of dissolved zinc. In this work, we present the synthesis of N-butylimidazolium-functionalized polysulfone (NBI-PSU)-based separators and evaluate their ability to selectively transport hydroxide over zincate. We then examine their impact on the cycling of high depth of discharge Zn/(Cu/Bi–MnO 2 ) batteries when inserted in between the cathode and anode. Initially, we establish our membranes’ selectivity by performing zincate and hydroxide diffusion tests, showing a marked improvement in zincate-blocking (D Zn (cm 2 /min): 0.17 ± 0.04 × 10 –6 for 50-PSU, our most selective separator vs 2.0 ± 0.8 × 10 –6 for Cellophane 350P00 and 5.7 ± 0.8 × 10 –6 for Celgard 3501), while maintaining similar crossover rates for hydroxide (D OH (cm 2 /min): 9.4 ± 0.1 × 10 –6 for 50-PSU vs 17 ± 0.5 × 10 –6 for Cellophane 350P00 and 6.7 ± 0.6 × 10 –6 for Celgard 3501). We then implement our membranes into cells and observe an improvement in cycle life over control cells containing only the commercial separators (cell lifetime extended from 21 to 79 cycles).

crossover↗

Dynamic Structure and Phase Behavior of a Block Copolymer Electrolyte under dc Polarization

There is an important consideration when designing lithium battery electrolytes for advanced applications is how the electrolyte facilitates ion transport at fast charge and discharge rates. Large current densities are accompanied by large salt concentration gradients across the electrolyte. Nanostructured composite electrolytes have been proposed to enable the use of high energy density lithium metal anodes, but many questions about the interplay between the electrolyte morphology and the salt concentration gradient that forms under dc polarization remain unanswered. To address these questions, we use an in situ small-angle X-ray scattering technique to examine the nanostructure of a polystyrene- block -poly(ethylene oxide) copolymer electrolyte under dc polarization with spatial and temporal resolution. In the quiescent state, the electrolyte exhibits a lamellar morphology. The passage of ionic current in a lithium symmetric cell leads to the formation of concurrent phases: a disordered morphology near the negative electrode, lamellae in the center of the cell, and coexisting lamellae and gyroid near the positive electrode. The most surprising result of this study was obtained after the applied electric field was turned off: a current-induced gyroid phase grows in volume for 6 h in spite of the absence of an obvious driving force. We show that this reflects the formation of localized pockets of salt-dense electrolyte, termed concentration hotspots, under dc polarization. Our methods may be applied to understand the dynamic structure of composite electrolytes at appreciable current densities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Patternable Mesoporous Thin Film Quantum Materials via Block Copolymer Self-Assembly: An Emergent Technology?

Recent developments in quantum materials hold promise for revolutionizing energy and information technologies. The use of soft matter self-assembly, for example, by employing block copolymers (BCPs) as structure directing or templating agents, offers facile pathways toward quantum metamaterials with highly tunable mesostructures via scalable solution processing. Here, we report the preparation of patternable mesoporous niobium carbonitride-type thin film superconductors through spin-coating of a hybrid solution containing an amphiphilic BCP swollen by niobia sol precursors and subsequent thermal processing in combination with photolithography. Spin-coated as-made BCP-niobia hybrid thin films on silicon substrates after optional photolithographic definition are heated in air to produce a porous oxide, and subsequently converted in a multistep process to carbonitrides via treatment with high temperatures in reactive gases including ammonia. Grazing incidence small-angle X-ray scattering suggests the presence of ordered mesostructures in as-made BCP-niobia films without further annealing, consistent with a distorted alternating gyroid morphology that is retained upon thermal treatments. Wide-angle X-ray scattering confirms the synthesis of phase-pure niobium carbonitride nanocrystals with rock-salt lattices within the mesoscale networks. Electrical transport measurements of unpatterned thin films show initial exponential rise in resistivity characteristic of thermal activation in granular systems down to 12.8 K, at which point resistivity drops to zero into a superconducting state. Magnetoresistance measurements determine the superconducting upper critical field to be over 16 T, demonstrating material quality on par with niobium carbonitrides obtained from traditional solid-state synthesis methods. Here. we discuss how such cost-effective and scalable solution-based quantum materials fabrication approaches may be integrated into existing microelectronics processing, promising the emergence of a technology with tremendous academic and industrial potential by combining the capabilities of soft matter self-assembly with quantum materials.

36 MATERIALS SCIENCE↗

Soft-Shear-Aligned Vertically Oriented Lamellar Block Copolymers for Template-Free Sub-10 nm Patterning and Hybrid Nanostructures

The template-free unidirectional alignment of lamellar block copolymers (l-BCPs) for sub-10 nm high-resolution patterning and hybrid multicomponent nanostructures is important for technological applications. Here we demonstrate a modified soft-shear directed self-assembly (SDSA) approach for aligning pristine l-BCPs and l-BCPs with incorporated polymer grafted nanoparticles (PGNPs), as well as the l-BCPs conversion to aligned gold nanowires, and hybrid of metallic gold nanowire and dielectric silica nanoparticle in the form of line-dot nanostructures. The smallest patterns have a half-pitch as small as 9.8 nm. In all cases, soft-shear is achieved using a high molecular mass polymer topcoat layer, with support on a neutral bottom layer. We also show that the hybrid line-dot nanostructures have a red-shifted plasmonic response in comparison to the neat gold nanowires. These template-free aligned BCPs and nanowires have potential use in nanopatterning applications and the line-dot nanostructures should be useful in the plasmonic sensing of biomolecules and other molecular species based on the plasmonic response of the nanowires.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrastable Gold Nanostars via Bottlebrush-like Block Copolymers

Gold (Au) nanostars are plasmonic nanostructures possessing potentials for small molecule detection, photocatalytic activities, and photothermal therapy. However, Au nanostars synthesized in the traditional way are often plagued by poor photo, thermal, and chemical stabilities. Here, we report an unconventional route to the synthesis of ultrastable colloidal Au nanostars enabled by bottlebrush-like block copolymers (BBCPs), dispensing with the need for Au seeds. Crafting of Au nanostars using BBCPs is rendered by bridging the latter with Au 3+ ions as cross-linkers that have multiple coordination sites. Notably, the presence of a covalently tethered polymer shell on the surface of Au nanostars (i.e., polymer-ligated Au nanostars) imparts remarkably high stability under high temperature and laser excitation over conventional cetyltrimethylammonium bromide (CTAB)-mediated Au nanostars. Due to enhanced laser stability, plasmonic fields near Au nanostars can be visualized under high laser fluence by ultrafast electron microscopy (UEM) without morphological degradation. Notably, the presence of insulating polystyrene chains does not compromise the plasmonic field distribution, with the highest field intensity observed along the star arms. In conclusion, the greatly improved long-term photo, thermal, and chemical stabilities make Au nanostars a prospective noble metal nanomaterial for a range of sensing applications.

Cellulose↗

Effect of Molecular Weight and Layer Thickness on Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films

Designing next-generation lightweight pulsed power devices hinges on understanding the factors influencing the energy storage performance of dielectric materials. Polymer dielectric films have a quadratic dependence of energy storage on the voltage breakdown strength and strategies to enhance the breakdown strength are expected to yield a path toward high energy storage densities. Highly stratified lamellar block copolymer (L-BCP) films of model polystyrene-b-polymethylmethacrylate (PS-b-PMMA) exhibited as much as ~50% enhancement in breakdown voltage (E BD ), (225 % increase in stored energy density, U~ E BD 2 ), compared to unordered as-cast L-BCP films. Such an energy density using amorphous polymer is on par with industry-standard semi-crystalline biaxially oriented polypropylene (BOPP), and as such a notable development in the field. This work develops a deeper understanding of the molecular mechanisms of E BD enhancement in L-BCP films, due to combination of interface formation and spatial isolation of the chain ends into segregated zones. We further confirm the role of chain ends in the breakdown process blending a low M n L-BCP with matched M n homopolymers to attain same layer spacing as neat L-BCP of higher M n . E BD shows a significant decrease at low homopolymer fractions due to increased net chain end density within swollen ordered L-BCP domains in wet-brush regime, followed by increased E BD due to layer thickness increase via segregated “interphase layer” formation by excess homopolymers. Notably, E BD of homopolymer swollen L-BCPs is always lower than neat L-BCP of the same domain spacing, due to overall adverse chain ends contribution from homopolymers. These findings provide important selection rules for L-BCPs for designing next-generation flexible electronics with high energy density solid-state BCP film capacitors.

36 MATERIALS SCIENCE↗

Inline Rolling Shear Alignment: Deposition and Long-Range Order of Block Polymer Templates in a Fast, Single-Step Process

We report the first demonstration of a rapid, single-step technique to align block polymer, thin-film nanostructures that is amenable to continuous speeds ≥10 mm/s. This method, termed Inline Rolling Shear Alignment (IRSA), uses an elastomeric roller coupled with an electric hysteresis brake to shear films before the casting solvent fully evaporates, and it can enable high throughput, large-area manufacturing of patterns such as nanowire templates. IRSA is adaptable to various polymer systems including diblock and triblock polymers, and a post-shear annealing step can yield high-quality nanostructures with orientation parameters >0.99 and defect densities as low as 5 defect-pairs/μm 2 . To demonstrate the effectiveness of IRSA, platinum nanowires were produced from this rapid deposition and alignment approach using poly(styrene-b-2-vinylpyridine), followed by open-air, atmospheric-pressure plasma etching. Furthermore, this integrated concept, with 50x faster operation than existing processes, could be leveraged for cost-effective manufacturing of macroscopically aligned nanostructures in roll-to-roll systems.

36 MATERIALS SCIENCE↗

Symmetry-Breaking and Self-Sorting in Block Copolymer-Based Multicomponent Nanocomposites

Co-assembly of inorganic nanoparticles (NPs) and nanostructured polymer matrix represents an intricate interplay of enthalpic or entropic forces. Particle size largely affects the phase behavior of the nanocomposite. Theoretical studies indicate that new morphologies would emerge when the particles become comparable to the soft matrix's size, but this has rarely been supported experimentally. By designing a multicomponent blend composed of NPs, block copolymer-based supramolecules, and small molecules, a 3-D ordered lattice beyond the native BCP's morphology was recently reported when the particle is larger than the microdomain of BCP. The blend can accommodate various formulation variables. In this work, when the particle size equals the microdomain size, a symmetry-broken phase appears in a narrow range of particle sizes and compositions, which we named the "train track" structure. In this phase, the NPs aligned into a 3-D hexagonal lattice and packed asymmetrically along the c axis, making the projection of the ac and the bc plane resemble train tracks. Computational studies show that the broken symmetry reduces the polymer chain deformation and stabilizes the metastable hexagonally perforated lamellar morphology. Given the mobility of the multicomponent blend, the system shows a self-sorting behavior: segregating into two macroscopic phases with different nanostructures based on only a few nanometers NP size differences. Smaller NPs form "train track" morphology, while larger NPs form a "simple hexagon" structure, where the NPs take a symmetric hexagonal arrangement. Detailed structural evolution and simulation studies confirm the systematic-wide cooperativity across different components, indicating the strong self-regulation of the multicomponent system.

"train track" morphology↗

Chain Redistribution Stabilizes Coexistence Phases in Block Copolymer Blends

The nanoscale morphologies of block copolymer (BCP) thin films are determined by chain architecture. Experimental studies of thin film blends of different BCP chain types have demonstrated that blending can stabilize new motifs, such as coexistence phases. Here, we deploy coarsegrained molecular dynamics (MD) simulations in order to better understand the self-assembly behavior of BCP blend thin films. Here, we consider blends of lamella- and cylinder-forming BCP chains, studying their morphological makeup, the chain distribution within the morphology, and the underlying polymer chain conformations. Our simulations show that there are local concentration deviations at the scale of the morphological objects that dictate the local structure, and that BCP chains redistribute within the morphology so as to stabilize the structure. Underlying these effects are measurable distortions in the BCP chain conformations. The conformational freedom afforded by BCP blending stabilizes defects and allows coexistence phases to appear, while also leading to kinetic trapping effects. These results highlight the power of blending in designing the morphology that forms.

36 MATERIALS SCIENCE↗

On-Demand Selection of the Latent Domain Orientation in Spray-Deposited Block Copolymer Thin Films

With their ability to self-assemble spontaneously into well-defined nanoscale morphologies, block copolymer (BCP) thin films are a versatile platform to fabricate functional nanomaterials. An important challenge to wider deployment of BCPs in nanofabrication is combining precise control over the nanoscale domain orientation in BCP assemblies with scalable deposition techniques that are applicable to large-area, curved, and flexible substrates. Here, in this study, we show that spray-deposited smooth films of a nominally disordered BCP exhibit latent orientations, which can be prescriptively selected by controlling solvent evaporation during spray casting. Subsequent solvent vapor annealing triggers assembly toward highly ordered cylindrical morphologies along the pathway determined by solvent evaporation in the prior spray deposition stage. Faster evaporation promotes assembly of vertically oriented cylinders spanning the entire film thickness (100–300 nm). In comparison, slow solvent evaporation permits intermicellar aggregation and incipient cylinder formation in solution, which induces horizontal cylinder assembly upon annealing. The evaporatively controlled latent orientation mechanism presented herein elucidates how nonequilibrium phenomena during casting govern successive self-assembly pathways and facilitates a versatile method to dictate the domain orientation of BCP thin films on demand on flexible and highly curved substrates or in distinct pattern areas on the same substrate.

36 MATERIALS SCIENCE↗

Toward controlling wetting hysteresis with nanostructured surfaces derived from block copolymer self-assembly

The synthesis of nanostructured surfaces via block copolymer (BCP) self-assembly enables a precise control of the surface feature shape within a range of dimensions of the order of tens of nanometers. Herein, this work studies how to exploit this ability to control the wetting hysteresis and liquid adhesion forces as the substrate undergoes chemical aging and changes in its intrinsic wettability. Via BCP self-assembly we fabricate nanostructured surfaces on silicon substrates with a hexagonal array of regular conical pillars having a fixed period (52 nm) and two different heights (60 and 200 nm), which results in substantially different lateral and top surface areas of the nanostructure. The wetting hysteresis of the fabricated surfaces is characterized using force–displacement measurements under quasistaic conditions and over sufficiently long periods of time for which the substrate chemistry and surface energy, characterized by the Young contact angle, varies significantly. The experimental results and theoretical analysis indicate that controlling the lateral and top area of the nanostructure not only controls the degree of wetting hysteresis but can also make the advancing and receding contact angles less susceptible to chemical aging. These results can help rationalize the design of nanostructured surfaces for different applications such as self-cleaning, enhanced heat transfer, and drag reduction in micro/nanofluidic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Parallel-in-Time Solution of Hyperbolic PDE Systems via Characteristic-Variable Block Preconditioning

We consider the parallel-in-time solution of both linear and nonlinear hyperbolic partial differential equation (PDE) systems in one spatial dimension. In the nonlinear setting, the discretized equations are solved with a preconditioned residual iteration based on a global linearization. The linear(ized) equation systems are approximately solved parallel-in-time using a block preconditioner applied in the characteristic variables of the underlying linear(ized) hyperbolic PDE. This change of variables is motivated by the observation that intervariable coupling between characteristic variables is weak, at least locally where spatio-temporal variations in the eigenvectors of the associated flux Jacobian are sufficiently small, while that between the original variables is not. For an ℓ-dimensional system of PDEs, applying the preconditioner consists of solving a sequence of ℓ scalar linear(ized)-advection-like problems, each associated with a different characteristic wave-speed in the underlying linear(ized) PDE. Furthermore, we approximately solve these linear advection problems using multigrid reduction-in-time (MGRIT); however, any other suitable parallel-in-time method could be used. Numerical examples are shown for the (linear) acoustics equations in heterogeneous media and for the (nonlinear) shallow water equations and Euler equations of gas dynamics with shocks and rarefactions. For many test problems, the solver converges in just a handful of iterations and with mesh-independent convergence rates.

97 MATHEMATICS AND COMPUTING↗

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗