Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “block copolymers”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14

Fabrication of model ultrafiltration membranes with uniform, high aspect ratio pores

Here, in this manuscript, we report the facile fabrication of large-area model membranes with highly uniform and high aspect ratio pores with diameters <20 nm. These membranes are useful for fundamental investigations of separation by size exclusion in the ultrafiltration regime, where species to be separated from solution have dimensions of 1–100 nm. Such investigations require membranes with narrow pores and high aspect ratios such that the Hagen–Poiseuille equation is followed, enabling well-known models such as the hindered transport model to be evaluated and other affecting factors to be ignored. We demonstrate that the sub-20 nm pores in the membrane are of sufficiently high aspect ratio such that water flux through the membrane is consistent with the Hagen–Poiseuille equation. The fabrication relies on self-assembling block copolymers to form uniform, densely packed patterns with sub-20 nm resolution, sequential infiltration synthesis to convert the block copolymer in situ into a mask with adequate contrast to etch pores with an aspect ratio >5, and low-resolution photolithography to transfer the pattern over a large area into a silicon nitride membrane. Model membranes with narrow pore-size distribution fabricated in this way provide the means to investigate parameters that impact size-selective ultrafiltration separations such as the relationships between solute or particle size and pore size, their distributions, and rejection profiles, and, therefore, test the validity or limits of separation models.

Chen, Wen↗

Hyperelastic binder for printed, stretchable electronics

Disclosed are compositions, devices, systems and fabrication methods for stretchable composite materials and stretchable electronics devices. In some aspects, an elastic composite material for a stretchable electronics device includes a first material having a particular electrical, mechanical or optical property; and a multi-block copolymer configured to form a hyperelastic binder that creates contact between the first material and the multi-block copolymer, in which the elastic composite material is structured to stretch at least 500% in at least one direction of the material and to exhibit the particular electrical, mechanical or optical property imparted from the first material. In some aspects, the stretchable electronics device includes a stretchable battery, biofuel cell, sensor, supercapacitor or other device able to be mounted to skin, clothing or other surface of a user or object.

Wang, Joseph↗

Mixed-Polarity Copolymers Based on Ethylene Oxide and Cyclic Carbonate: Insights into Li-Ion Solvation and Conductivity

Here, this study investigates the relationship between polarity and ionic conductivity in random and block copolymer electrolytes comprising highly flexible oligo(ethylene oxide) methyl ether methacrylate (OEM) and highly polar but glassy glycerol carbonate methacrylate (GCMA) monomers, blended with either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium triflate. Interestingly, the high polarity of GCMA did not significantly enhance ionic dissociation, and the random copolymers (POEM-r-PGCMA) showed similar or lower ionic conductivities than the POEM homopolymer. Further analysis revealed that Li + only interacts with OEM and its counterion, not with GCMA. The less-intermixed and weakly phase-separated block copolymer (POEM-b-PGCMA) exhibited even lower conductivities than the random copolymer. Our results suggest that Li + solvation occurs only in the POEM-rich phase and that the larger PGCMA regions, depleted of Li + , disrupt long-range ion transport. These findings provide valuable insights into the design of polymer electrolytes and how segmental mobility and functional groups with contrasting polarities affect ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Characterization of Polymeric Pore Former Microspheres using Modified Polymer Resin

Porosity in polymer parts is often desired to improve mechanical properties. Individual pores must be small enough that bulk mechanical properties are retained but significant enough to reduce the density of the material. Filler materials can be incorporated into polymer matrices and subsequently removed to create voids. The materials used to create the voids are known as pore-formers. The present research aims to create spherical pores in a silicone matrix by inserting and removing core materials or fillers post-cure. A method was developed to incorporate pore formers into an uncured polymer resin and remove the materials from the matrix. Polyethylene Glycol (PEG) and Polylactic Acid (PLA) microspheres are created and incorporated into silicone matrices as pore formers. Microspheres with controllable size distributions are formed via ultrasonic spray pyrolysis and emulsion formation. Microspheres are removed from the matrix by solvent extraction and calcination. PLA microspheres were modified by hydroxyl addition to the surface to study their solubility in water. PEG-PLA block copolymers are also synthesized and investigated, comparing their physical and chemical properties to the monomers to identify whether the block copolymer microspheres will be more easily removable than their monomeric microspheres. Moreover, other properties including thermal stability, rheology, and mechanical response are studied. The present dissertation provides a comprehensive understanding of the synthesis and characterization of PEG and PLA-based pore formers, toward the future development of feedstock for additive manufacturing porous structures.

Damptey, Ransford↗

Swelling-Assisted Sequential Infiltration Synthesis of Nanoporous ZnO Films with Highly Accessible Pores and Their Sensing Potential for Ethanol

Here, we report a swelling-assisted sequential infiltration synthesis (SIS) approach for the design of highly porous zinc oxide (ZnO) films by infiltration of block copolymer templates such as polystyrene-block- polyvinyl pyridine with inorganic precursors followed by UV ozone-assisted removal of the polymer template. We show that porous ZnO coatings with the thickness in the range between 140 and 420 nm can be obtained using only five cycles of SIS. The pores in ZnO fabricated via swelling-assisted SIS are highly accessible, and up to 98% of pores are available for solvent penetration. The XPS data indicate that the surface of nanoporous ZnO films is terminated with -OH groups. Density functional theory calculations show a lower energy barrier for ethanol-induced release of the oxygen restricted depletion layer in the case of the presence of -OH groups at the ZnO surface, and hence, it can lead to higher sensitivity in sensing of ethanol. We monitored the response of ZnO porous coatings with different thicknesses and porosities to ethanol vapors using combined mass-based and chemiresistive approaches at room temperature and 90 °C. The porous ZnO conformal coatings reveal a promising sensitivity toward detection of ethanol at low temperatures. In conclusion our results suggest the excellent potential of the SIS approach for the design of conformal ZnO coatings with controlled porosity, thickness, and composition that can be adapted for sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Designing Anion-Exchange Ionomers with Oriented Nanoscale Phase Separation at a Silver Interface

We report performance of polymer electrolyte-based energy systems is significantly impacted by transport within the electrode catalyst layer, where ionomer thin films coat catalyst particles. Proton exchange ionomer thin films have been thoroughly characterized, but few studies have critically examined anion-exchange ionomer (AEI) thin films. Further, none have reported nanoscale phase separation for hydrocarbon AEIs, which is critical to mitigate transport resistances. In this work, a set of hydrocarbon-based AEIs with nanoscale phase separation are developed from tunable block copolymer systems composed of polyisoprene (PIp) and polychloromethylstyrene (PCMS). The effect of the PIp/PCMS ratio, architecture, and thickness on the thin-film morphology of the neutral block copolymer precursors on silicon and silver substrates is investigated using grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM). AEIs are prepared by quaternizing with trimethylamine or methylpiperidine and their cation-dependent morphology is characterized at 60 °C and 95% RH. A perpendicularly aligned morphology is observed on silver, while no phase separation is observed on silicon, indicating that silver-polymer interfacial interactions drive phase separation. After quaternization, dipole-dipole interactions induce some disorder, but nanoscale phase separation is still maintained. GISAXS patterns are modeled using a Unified Fit approach to understand water uptake and swelling, and recommendations for AEI design are presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Miktoarm Star Polymers: Synthesis and Applications

Polymers with precisely controlled structure and function are in high demand across a diverse array of applications spanning the life sciences and nanotechnology. One prototypical example is a class of branched block copolymers known as miktoarm stars (μ-stars), which contain two or more arm compositions connected at a common junction. Miktoarm stars have attracted considerable attention since their physical properties can be different from conventional linear block copolymers. This perspective highlights the latest developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools used to avoid common preparation pitfalls and tailor properties for emerging applications. Furthermore, our contemporary perspective on μ-star polymers is a resource for inspiring future research into this exciting class of materials at the intersection of chemistry, physics, and advanced technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Correlations and Partial Ionicities in the Lamellar Phases of Block Copolymeric Ionic Liquids

Recently, significant interest has arisen on the impact of dynamical ion correlations on the conductivity and transport properties of polymeric electrolyte materials. It has been hypothesized that confining ion motion to narrow channels may reduce such ion correlations and enhance the resulting ionic conductivity. Motivated by such considerations, in this study we used a multiscale simulation framework to study the dynamical ion correlations in the microphase-separated lamella phase of block copolymeric ionic liquids and compare with the corresponding results for homopolymeric systems. We probed the influence of ion correlations through the partial ionicity, Δ, which quantifies the ratio of true conductivity to the ideal, Nernst–Einstein conductivity for the anion-related contributions. Consistent with our original hypothesis, our results demonstrate that the partial ionicity relating to the mobile anions is much larger in the lamella phases of block copolymers compared to that in homopolymers. Analysis of the distinct conductivity contributions demonstrates that such results arise as a result of an intricate compensation among the nonideal dynamical correlations relating to anions in lamella phases. Overall, our results suggest that self-assembled phases of block copolymers may provide an avenue to tune the dynamical ion correlations in polymer electrolyte systems.

36 MATERIALS SCIENCE↗

Mechanisms of Metal Additive-Induced Ordering During SNIPS Membrane Formation

Isoporous membranes can be fabricated by combining self-assembly with nonsolvent induced phase separation (SNIPS) using an amphiphilic block copolymer like polystyrene-b-poly(4-vinylpyridine) (SV). Poly(4-vinylpyridine) (V) is known to complex with metal salts, which are hypothesized to stabilize solution ordering and preserve structure during casting. We explored how the molar ratio of metal additive to the poly(4-vinylpyridine) block affected the final membrane morphology via scanning electron microscopy (SEM). Dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and in situ grazing-incidence SAXS were used to track changes in solution ordering and chain conformation as a function of the molar ratio of the additive to the V block. Additives induced aggregation, promoted the formation of more compact conformations in solution, and facilitated micelle ordering onto lattices at optimal ratios. Furthermore, these experimental results were supported by random phase approximation calculations, which helped explain how the thermodynamic order–disorder transition shifts with additive binding strength. Stronger additive–polymer interactions reduced the block copolymer volume fraction required for ordering in solution, allowing ordered domains to form at lower polymer concentrations.

Additives↗

Virgin-like High-Density Polyethylene from Recycled Mixed Polyolefins

Reported herein is the compatibilization of mixed polyolefins containing a rheology modifier (M-PO RM ) derived from municipal solid waste (MSW) by using different types of compatibilizers. One compatibilizer was produced “in situ” during reactive extrusion (REX), and the other compatibilizers were commercial styrenic block copolymer and maleated polymer-based compatibilizers. Both “in situ” and commercial compatibilizers were first used in laboratory-controlled polyolefins containing a rheology modifier (denoted as L-PO RM ) and were investigated for their mechanical properties. The study was then extended to a rheology modifier containing recycled mixed polyolefins (M-PO RM ), where the effects of both compatibilizers were evaluated. Compared to the in situ and other commercial compatibilizers, the styrenic block copolymer offered superior performance, as it enabled the synthesis of virgin-like high-density polyethylene (HDPE) from the M-PO RM . The findings suggest that M-PO RM can be transformed into blends with virgin HDPE-like properties, thus offering an industrially relevant approach for the re- and upcycling of mixed polyolefins. Finally, the M-PO RM pellets with uniform MFI and good mechanical properties can be used as injection mold feedstocks for different applications such as in the construction and automotive sectors.

compatibilization↗

Implementing the donor–acceptor approach in electronically conducting copolymers via electropolymerization

Electropolymerization has become a convenient method for synthesizing and characterizing complex organic copolymers having intrinsic electronic conductivity, including the donor (D)–acceptor (A) class of electronically conducting polymers (ECPs). This review begins with an introduction to the electrosynthesis of common second-generation ECPs. The information obtainable from electroanalytical studies, charge carriers such as polarons (positive and negative) and bipolarons (positive and negative) and doping will be discussed. The evolutionary chain of ECPs is then presented. ECPs comprising electron-rich D and electron-deficient A moieties have been shown to possess intrinsic electronic conductivity and unique optical and electronic properties. They are third generation ECPs and electropolymerization of mixtures of D and A leads to stoichiometrically controlled block copolymers. These D–A type ECPs are discussed on the basis of selected representative materials. Since the discovery of electropolymerization as a powerful tool to synthesize copolymers of conjugated monomers with a pre-determined ratio of D and A repeat units present in the polymer, the field of D–A type ECPs has grown considerably and the literature available since 2004 to 2021 is summarized and tabulated. Electronic and optical properties of the materials determined by computational chemistry are presented. The data obtained from electrochemical and optical methods are compared with those obtained from computational methods and reasons for discrepancies are given. The literature on the concept of electropolymerization extended to synthesizing triblock and many-block copolymers is reviewed. Finally, applications of D–A polymers in optoelectronic devices (organic solar cells and field-effect transistors) and in bio-imaging are explained quoting appropriate examples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Resolution Imaging of Unstained Polymer Materials

Electron microscopy has played an important role in polymer characterization. Traditionally, electron diffraction is used to study crystalline polymers while transmission electron microscopy is used to study microphase separation in stained block copolymers and other multiphase systems. We describe developments that eliminate the barrier between these two approaches - it is now possible to image polymer crystals with atomic resolution. The focus of this Review is on high-resolution imaging (30 Å and smaller) of unstained polymers. Recent advances in hardware allow for capturing numerous (as many as 105) low-dose images from an unperturbed specimen; beam damage is a significant barrier to high-resolution electron microscopy of polymers. Machine-learning-based software is then used to sort and average the images to retrieve pristine structural information from a collection of noisy images. Acknowledging the heterogeneity in polymer samples prior to averaging is essential. Molecular conformations in a wide range of amphiphilic block copolymers, polymerized ionic liquids, and conjugated polymers can be gleaned from two-dimensional projections (2D), three-dimensional (3D) tomograms, and four-dimensional (4D) scanning transmission electron microscopy (STEM) data sets where 2D diffraction patterns are taken as a function of position. Some methods such as phase contrast STEM have been used to image closely related materials such as metal-organic frameworks but not polymers. With improvements in hardware and software, such methods may soon be applied to polymers. Our goal is to provide a comprehensive understanding of the strategies toward the high-resolution imaging of radiation sensitive polymer materials at different length scales.

36 MATERIALS SCIENCE↗

End-exclusion zones in strongly stretched, molten polymer brushes of arbitrary shape

Theories of strongly stretched polymer brushes, particularly the parabolic brush theory, are valuable for providing analytically tractable predictions for the thermodynamic behavior of surface-grafted polymers in a wide range of settings. Furthermore, the parabolic brush limit fails to describe polymers grafted to convex curved substrates, such as the surfaces of spherical nanoparticles or the interfaces of strongly segregated block copolymers. It has previously been shown that strongly stretched curved brushes require a boundary layer devoid of free chain ends, requiring modifications of the theoretical analysis. While this “end-exclusion zone” has been successfully incorporated into the descriptions of brushes grafted onto the outer surfaces of cylinders and spheres, the behavior of brushes on surfaces of arbitrary curvature has not yet been studied. We present a formulation of the strong-stretching theory for molten brushes on the surfaces of arbitrary curvature and identify four distinct regimes of interest for which brushes are predicted to possess end-exclusion zones, notably including regimes of positive mean curvature but negative Gaussian curvature. Through numerical solutions of the strong-stretching brush equations, we report predicted scaling of the size of the end-exclusion zone, the chain end distribution, the chain polarization, and the free energy of stretching with mean and Gaussian surface curvatures. Through these results, we present a comprehensive picture of how the brush geometry influences the end-exclusion zones and exact strong-stretching free energies, which can be applied, for example, to model the full spectrum of brush geometries encountered in block copolymer melt assembly.

36 MATERIALS SCIENCE↗

Membrane-Induced Vanadium Crossover-Blocking Polybenzimidazole Copolymer with Exceptional Proton Selectivity

Broad deployment of redox flow batteries is hindered, in part, due to the lack of highly selective ion-exchange membranes with high proton conductivity. We report a post-functionalization strategy for polybenzimidazole copolymer (PBI-co) membranes by a reacting mixture of concentrated sulfuric and phosphoric acids that led to improved membrane selectivity while retaining high proton conductivity. Fourier-transform infrared spectroscopy confirmed successful sulfonation and protonation of benzimidazole functionalities. PBI-co exhibits a very high room-temperature proton conductivity of 0.138 S cm -1 , as measured by electrochemical impedance spectroscopy. PBI-co also demonstrates electromigration crossover mitigation under applied current densities up to 500 mA cm -2 , and voltage pulses up to 1.4 V, while also inhibiting diffusion-driven vanadium crossover for over 20 days. Single-cell vanadium flow battery testing on post-functionalized PBI-co further confirms state-of-the-art battery performance with an ~99.5% Coulombic efficiency at 100 mA cm -2 and an area-specific resistance of ~20 mO cm 2 lower than Nafion-212 membrane.

25 ENERGY STORAGE↗