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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.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Bulk Glassy GeTe 2 : A Missing Member of the Tetrahedral GeX 2 Family and a Precursor for the Next Generation of Phase-Change Materials

Vitreous germanium disulfide GeS 2 and diselenide GeSe 2 belong to canonical chalcogenide glasses extensively studied over the past half century. Their high-temperature orthorhombic polymorphs are congruently melting compounds, and the tetrahedral crystal and glass structure is largely preserved in the melt. In contrast, the ditelluride counterpart is absent in the Ge-Te phase diagram, which shows only a single compound, monotelluride GeTe. Phase-change materials based on GeTe have become a technologically important class of solids, and their structure and properties are also widely studied. Surprisingly, very scarce information is available for alloys having GeTe 2 stoichiometry. Using a fast quenching procedure in silica capillaries, high-energy X-ray diffraction, and Raman spectroscopy supported by first-principles simulations, we show that bulk glassy GeTe 2 differs substantially from the lighter GeX 2 members, revealing 46% of trigonal germanium, 31% of three-fold coordinated tellurium, and only 20% of edge-sharing tetrahedra or pyramids. The fraction of homopolar Ge-Ge bonds is low; however, the population of dominant Te-Te dimers and Te n oligomers, n <= 10, appears to be significant. The complex structural and chemical topology of g-GeTe 2 is directly related to the thermodynamic metastability of germanium ditelluride, schematically represented by the following reaction: GeTe 2 $\rightleftarrows$ GeTe + Te. Disproportionation is complete above liquidus in the temperature range of semiconductor-metal transition, and the dense metallic GeTe 2 liquid, mostly consisting of five-fold coordinated Ge species, exhibits high fluidity, strong fragility (m = 99 ± 5), and presumably a fast structural transformation rate combined with low atomic mobility in the vicinity of the glass transition temperature, favorable for reliable long-term data retention in nonvolatile memories. The observed and predicted characteristic features make GeTe 2 a promising precursor for the next generation of phase-change materials, especially coupled with additional metal doping, depolymerizing the tetrahedral interconnected glass network and accelerating (sub)nanosecond crystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A high-solid DES pretreatment using never-dried biomass as the starting material: towards high-quality lignin fractionation

This study investigated a high-solid diol deep eutectic solvent (DES) pretreatment using a wet substrate as the starting material. This pretreatment led to a remarkable glucan saccharification of 94.8% with efficient lignin and xylan removal (as high as 63.1% and 73.0%, respectively). Here the chemical structures of the substrates were analyzed comprehensively to reveal the impact of the pretreatment. In addition, over 90% of the removed lignin was recovered from the pretreated liquid, which exhibited a well-preserved β-O-4 structure (46–56/100Ar). The protection mechanism of our DES was investigated by 2D HSQC NMR, GPC, and 31 P NMR analysis. This study emphasized that diol-based DES pretreatment of undried lignocellulosic biomass at a high-solid loading can significantly utilize both carbohydrates and lignin fractions with high saccharification yields and high-quality lignin as a co-product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tutorial on In Situ and Operando (Scanning) Transmission Electron Microscopy for Analysis of Nanoscale Structure–Property Relationships

In situ and operando (scanning) transmission electron microscopy [(S)TEM] is a powerful characterization technique that uses imaging, diffraction, and spectroscopy to gain nano-to-atomic scale insights into the structure–property relationships in materials. This technique is both customizable and complex because many factors impact the ability to collect structural, compositional, and bonding information from a sample during environmental exposure or under application of an external stimulus. In the past two decades, in situ and operando (S)TEM methods have diversified and grown to encompass additional capabilities, higher degrees of precision, dynamic tracking abilities, enhanced reproducibility, and improved analytical tools. Much of this growth has been shared through the community and within commercialized products that enable rapid adoption and training in this approach. This tutorial aims to serve as a guide for students, collaborators, and nonspecialists to learn the important factors that impact the success of in situ and operando (S)TEM experiments and assess the value of the results obtained. As this is not a step-by-step guide, readers are encouraged to seek out the many comprehensive resources available for gaining a deeper understanding of in situ and operando (S)TEM methods, property measurements, data acquisition, reproducibility, and data analytics.

(S)TEM↗
DOE OSTI2024

Role of Solvent in the Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces

Abstract A controlled growth of two‐dimensional (2D) π‐conjugated metal‐organic frameworks (MOFs) on solid substrates can open exciting opportunities for the application of 2D MOFs as optoelectronic devices. Some factors like solvent composition and type of substrates are known to influence the properties of solution‐processed 2D MOF crystals; however, a mechanistic understanding of how interactions between solvent, substrate, and precursors affect heterogeneous nucleation has been limited. Here, it is reported that the structure of Ni‐catecholate (Ni‐CAT‐1) MOFs at a solid–liquid interface is controlled by solvent–substrate and solvent–MOF precursor interactions. Specifically, the structure of the MOF film can be controlled by varying the affinity of the solvent to the substrate. As a fraction of N , N ‐dimethylformamide (DMF) in a binary solvent mixture of water and DMF increases, the arrangement of Ni‐CAT‐1 crystals varies from vertically aligned nanorods to the graphite substrate to less ordered nanorods with the lower initial nucleation number density of Ni‐CAT‐1 crystals on the surface.

2D materials↗
DOE OSTI2023

Low-temperature liquid-phase formation of environmentally stable copper halide nanocrystal superlattices and their application to anticounterfeiting patterns

Nanocrystal superlattices have the potential to create a new class of semiconductor materials by combining the photophysical properties of individual nanocrystals with bulk-like structure performance. However, the principles underlying the direct formation of superlattices in liquid phase have not been thoroughly investigated, particularly, those consisting of exciton self-trapping metal halides. Here, in this work, we explore the formation of Cs 3 Cu 2 Br 5 nanocrystal superlattices via liquid-phase crystallization of growing nanocrystals over a reaction period of only a few seconds. Importantly, the reaction temperature and the precursor concentration were found to be key parameters governing the concomitant nanocrystal growth and superlattice formation. The resulting Cs 3 Cu 2 Br 5 superlattices had a well-defined face-centered cubic structure and emitted a single-band bright blue emission when exposed to 280 nm light. Owing to their advantages, such as low toxicity, reabsorption-free, narrow absorption, strong emission, and high environmental stability, the Cs 3 Cu 2 Br 5 superlattices were applicable to anti-counterfeiting applications. Our findings shed light on the liquid-phase assembly of nanocrystals into superlattices and highlight the potential applications of the superlattices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

CP2K: An Electronic Structure and Molecular Dynamics Software Package - Quickstep: Efficient and Accurate Electronic Structure Calculations

CP2K is an open source electronic structure and molecular dynamics software package to perform atomistic simulations of solid-state, liquid, molecular and biological systems. It is especially aimed at massively-parallel and linear-scaling electronic structure methods and state-of-the-art ab-initio molecular dynamics simulations. Excellent performance for electronic structure calculations is achieved using novel algorithms implemented for modern high-performance computing systems. This review revisits the main capabilities of CP2K to perform efficient and accurate electronic structure simulations. The emphasis is put on density functional theory and multiple post-Hartree-Fock methods using the Gaussian and plane wave approach and its augmented all-electron extension. TDK has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement No. 716142). VRR has been supported by the Swiss National Science Foundation in the form of Ambizione grant No. PZ00P2 174227 and RZK by the Natural Sciences and Engineering Research Council of Canada (NSERC) through Discovery Grants (RGPIN-2016-0505). GKS and CJM are supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. UK based work was funded under the embedded CSE programme of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk), grants eCSE03-011, eCSE06-6, eCSE08-9, eCSE13-17 and the EPSRC (EP/P022235/1) grant “Surface and Interface Toolkit for the Materials Chemistry Community". Computational resources were provided by the Swiss National Supercomputing Centre (CSCS) and Compute Canada. The generous allocation of computing time on the FPGA-based supercomputer “Noctua" at PC2 is kindly acknowledged.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Poly(ionic liquid)s with Dicationic Pendants as Gas Separation Membranes

Poly(norbornene)s and poly(ionic liquid)s are two different classes of attractive materials, which are known for their structural tunability and thermal stabilities, and have been extensively studied as gas separation membranes. The incorporation of ionic liquids (ILs) into the poly(norbornene) through post-polymerization has resulted in unique materials with synergistic properties. However, direct polymerization of norbornene-containing IL monomers as gas separation membranes are limited. To this end, a series of norbornene-containing imidazolium-based mono- and di-cationic ILs (NBM-mIm and NBM-DILs) with different connectivity and spacer lengths were synthesized and characterized spectroscopically. Subsequently, the poly(NBM-mIm) with bistriflimide [Tf2N−] and poly([NBM-DILs][Tf2N]2) comprising homo-, random-, and block- (co)polymers were synthesized via ring-opening metathesis polymerization using the air-stable Grubbs second-generation catalyst. Block copolymers (BCPs), specifically, [NBM-mIM][Tf2N] and [NBM-ImCnmIm] [Tf2N]2 (n = 4 and 6) were synthesized at two different compositions, which generated high molecular weight polymers with decent solubility relative to homo- and random (co)polymers of [NBM-DILs] [Tf2N]2. The prepared BCPs were efficiently analyzed by a host of analytical tools, including 1H-NMR, GPC, and WAXD. The successfully BCPs were cast into thin membranes ranging from 47 to 125 μm and their gas (CO2, N2, CH4, and H2) permeations were measured at 20 °C using a time-lag apparatus. These membranes displayed modest CO2 permeability in a non-linear fashion with respect to composition and a reverse trend in CO2/N2 permselectivity was observed, as a usual trade-off behavior between permeability and permselectivity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Assessment of Precipitating Marine Stratocumulus Clouds in the E3SMv1 Atmosphere Model: A Case Study from the ARM MAGIC Field Campaign

This paper presents a process-oriented evaluation of precipitating stratocumulus and its transition to cumulus in version 1 of the Energy Exascale Earth System Model (E3SMv1) using comprehensive case-study observations from a field campaign of the Atmospheric Radiation Measurement program (ARM). The E3SMv1 single-column model (SCM) of the marine boundary layer and its low clouds and precipitation are compared to observations including subcloud drizzle retrievals from a combination of Doppler radar and lidar backscatter measurements. Additionally, the SCM is also compared to a large-eddy simulation (LES) of the same case. The combination of advanced remote sensing observations and LES is a powerful framework to evaluate the physical parameterizations of large-scale models. Given the observed large-scale environment, the E3SMv1 SCM realistically represents the evolution of clouds and boundary layer structure during the stratocumulus-to-cumulus transition. The model well simulates the liquid water path and its diurnal cycle in the stratocumulus period as well as the two-layer vertical thermodynamic structure and lower cloud fraction in the transition period. E3SMv1’s success in simulating the cloud in the stratocumulus period permitted examination of its precipitation processes. Here problems were identified with E3SMv1 producing an unrealistically small subcloud precipitation fraction, an unrealistic double peak in the vertical profiles of precipitation mass, and drizzle that evaporates too close to the surface. Further model diagnostics determined that these unrealistic characteristics resulted from an overly long microphysics time step and an unrealistic parameterization of the precipitation fraction. These results imply that careful consideration of these issues is needed in order to better simulate precipitation processes in marine stratocumulus.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Helfrich-Hurault elastic instabilities driven by geometrical frustration

Here, the Helfrich-Hurault (HH) elastic instability is a well-known mechanism behind patterns that form as a result of strain upon liquid crystal systems with periodic ground states. In the HH model, layered structures undulate and buckle in response to local, geometric incompatibilities in order to maintain the preferred layer spacing. Classic HH systems include cholesteric liquid crystals under electromagnetic field distortions and smectic liquid crystals under mechanical strains, where both materials are confined between rigid substrates. However, richer phenomena are observed when undulation instabilities occur in the presence of deformable interfaces and variable boundary conditions. Understanding how the HH instability is affected by deformable surfaces is imperative for applying the instability to a broader range of materials. In this review, the HH mechanism is reexamined and special focus is given to how the boundary conditions influence the response of lamellar systems to geometrical frustration. Lamellar liquid crystals confined within a spherical shell geometry are used as the model system. Made possible by the relatively recent advances in microfluidics within the past 15 years, liquid crystal shells are composed entirely of fluid interfaces and have boundary conditions that can be dynamically controlled at will. Past and recent work that exemplifies how topological constraints, molecular anchoring conditions, and boundary curvature can trigger the HH mechanism in liquid crystals with periodic ground states is examined. The review ends by identifying similar phenomena across a wide variety of materials, both biological and synthetic. The fact that the HH mechanism is a generic and often overlooked response of periodic materials to geometrical frustration is highlighted.

42 ENGINEERING↗
DOE OSTI2020

Quantum liquid from strange frustration in the trimer magnet Ba4Ir3O10

Abstract Quantum spin systems such as magnetic insulators usually show magnetic order, but such classical states can give way to quantum liquids with exotic entanglement through two known mechanisms of frustration: geometric frustration in lattices with triangle motifs, and spin-orbit-coupling frustration in the exactly solvable quantum liquid of Kitaev’s honeycomb lattice. Here we present the experimental observation of a new kind of frustrated quantum liquid arising in an unlikely place: the magnetic insulator Ba 4 Ir 3 O 10 where Ir 3 O 12 trimers form an unfrustrated square lattice. The crystal structure shows no apparent spin chains. Experimentally we find a quantum liquid state persisting down to 0.2 K that is stabilized by strong antiferromagnetic interaction with Curie–Weiss temperature ranging from −766 to −169 K due to magnetic anisotropy. The anisotropy-averaged frustration parameter is 2000, seldom seen in iridates. Heat capacity and thermal conductivity are both linear at low temperatures, a familiar feature in metals but here in an insulator pointing to an exotic quantum liquid state; a mere 2% Sr substitution for Ba produces long-range order at 130 K and destroys the linear-T features. Although the Ir 4+ (5d 5 ) ions in Ba 4 Ir 3 O 10 appear to form Ir 3 O 12 trimers of face-sharing IrO 6 octahedra, we propose that intra-trimer exchange is reduced and the lattice recombines into an array of coupled 1D chains with additional spins. An extreme limit of decoupled 1D chains can explain most but not all of the striking experimental observations, indicating that the inter-chain coupling plays an important role in the frustration mechanism leading to this quantum liquid.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Predicting Saturated Hydraulic Conductivity over Time for Degrading Saltstone Vault Concrete - 20376

At the Savannah River Site (SRS), low-level liquid tank waste is mixed with cementitious materials to produce a solid, monolithic waste form referred to as saltstone. The liquid saltstone mixture is pumped into massive concrete structures referred to as saltstone disposal units (SDUs) for curing and long-term storage. SDUs are vaults made of high performance concrete forming a barrier between saltstone and the surrounding environment. Predicting the long-term performance of SDU vault concrete, as well as the saltstone material itself, is critical to understanding the potential releases of radionuclides to the surrounding environment as described in the Saltstone Disposal Facility (SDF) performance assessment (PA). The hydraulic conductivity profile for SDU vault concrete was conservatively assumed to degrade linearly from the initial saturated hydraulic conductivity of the intact concrete over a long period of time. The initial hydraulic properties of saturated SDU vault concrete have been measured, and the final hydraulic properties of degraded vault concrete are assumed to be the same as the porous backfill material that will surround the vault after closure. The assumed final condition of the vault concrete is also conservative in that it provides a greater estimate of water penetration through the vault than would generally be expected. Therefore, insights that provide more realistic but conservative estimates as to how degradation processes may change the hydraulic properties of the SDU vault concrete, the time dependent relationship of the vault concrete hydraulic properties to degradation (and thus time), and the final hydraulic properties of the vault concrete provides useful additions to the SDF PA. This paper focuses on the assumption that the saltstone vault concrete saturated hydraulic conductivity would decrease linearly as a function of degradation time; this assumption resulted from a worst-case, weighted (by relative layer thickness), arithmetic average of intact and backfill material hydraulic conductivities representing flow parallel to a layered system. This research indicates that the effective saturated hydraulic conductivity of the degraded SDU vault concrete should be based on the relative thickness-weighted geometric mean of the intact and degraded layers hydraulic conductivities. This alternative, which is supported extensively in the relevant literature and evaluated in this paper, leads to a more realistic and defensible estimate of the effective saturated hydraulic conductivity in degraded vault concrete while remaining conservative. The impact of using the more realistic estimate of the effective saturated hydraulic conductivity for the degraded concrete decreases the effective saturated hydraulic conductivity by up to several orders of magnitude for early times (i.e., when the SDU vault concrete is assumed degraded via sulfate attack and carbonation). This revised estimate of the effective saturated hydraulic conductivity has been implemented in the recently revised SDF PA. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Structural Distortions and Short‐Range Magnetism in a Honeycomb Iridate Cu 3 ZnIr 2 O 6

Layered honeycomb iridates receive significant attention in the materials chemistry and physics fields due to the relevance of their crystal structures to the Kitaev model of a quantum spin liquid (QSL). In quest of liquid‐like magnetic ground state signatures, first‐generation alkali metal iridates A 2 IrO 3 ≡ A 3 [AIr 2 ]O 6 (A = Li, Na) and second‐generation iridates T 3 [AIr 2 ]O 6 ( T = Cu, Ag, H) are developed. T 3 [AIr 2 ]O 6 is synthesized from A 3 [AIr 2 ]O 6 via metathesis reactions replacing alkali ions located between honeycomb layers. Herein, the next level of chemical and structural complexity is introduced by synthesizing the honeycomb iridate, Cu 3 ZnIr 2 O 6 , in which alkali ions between and within the honeycomb layers are both selectively exchanged with two different transition metals. Analysis of powder X‐Ray diffraction data reveals corrugation of the honeycomb layers in Cu 3 ZnIr 2 O 6 that hinders complete magnetic frustration and results in a spin glass behavior observed from magnetization and specific heat data. Thus, Cu 3 ZnIr 2 O 6 represents yet another model, which broadens understanding of intricate relationships between intralayer distortions and magnetism of prospective Kitaev QSL compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Emergent mystery in the Kondo insulator samarium hexaboride

Samarium hexaboride (SmB 6 ) is an example of a Kondo insulator, in which strong electron correlations cause a band gap to open. SmB 6 hosts both a bulk insulating state and a conductive surface state. Within a Fermi-liquid framework, the strongly correlated ground-state electronic structure can be mapped to a simple state resembling a topological insulator. Although uncertainties remain, many experiments provide compelling evidence that the conductive surface states have a topological origin. However, the bulk behavior is less well understood and some experiments indicate bulk in-gap states. This has inspired the development of many theories that predict the emergence of new bulk quantum phases beyond Landau’s Fermi-liquid model. We review the current progress on understanding both the surface and the bulk states, especially the experimental evidence for each. A mystery centres on the existence of the bulk in-gap states and why they appear in some experiments but not others. Adding to the mystery is why quantum oscillations in SmB6 appear only in magnetization but not in resistivity. Here, we conclude by elaborating on three questions: why SmB 6 is worth studying, what can be done to move forwards and what other correlated insulators could give additional insight.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Assessing the Effect of Explicit Polarizability on Models of Carbon Dioxide Solvation in Ionic Liquids

Ionic liquids are an important possible carbon capture material because of their anomalously high sorption selectivity for carbon dioxide over other gases common in air. Many research groups have investigated the molecular origins of this property and provided important insights, including using 1D and 2D-IR spectroscopy. Molecular dynamics simulations have been indispensable to the interpretation of these experiments. In prior molecular dynamics simulation work, charge-scaled force fields have typically been used to provide a mean-field treatment of effects vital to ionic liquid systems such as charge transfer and polarization. Here, we compare models of carbon dioxide solvated in ionic liquids with explicit polarization to models of the same with implicit polarizability through charge-scaling. We calculate structural, dynamical, and spectroscopic properties, and make comparisons to the same items measured in experiment. In this study, we focus on two ionic liquids: 1-butyl-3- methylimidazolium (BMIM + ) paired with bis(trifluoromethane sulfonyl imide) (Tf 2 N − ) and 1-butyl-3-methylimidazolium (BMIM+) paired with hexafluorophosphate (PF 6 − ). We find that many structural, dynamical, and spectroscopic properties are changed when polarization is modeled explicitly. We also find that explicit polarizability softens local ion cages around the carbon dioxide and that the long-time diffusion of the carbon dioxide is gated by the reorganization of the ionic liquid molecules. Comparisons to experiment show modest improvement of many observables compared with experiment for the explicitly polarizable model over the charge-scaled model. Overall, our results show that charge-scaled force fields are likely sufficient to compute spectroscopic properties of carbon dioxide in ionic liquids and suggest some interpretive rules for understanding their structural and dynamical properties. Those using charge-scaled force fields should generally assume that the ion cages around solutes such as carbon dioxide are too stiff and cation-rich in their models and adjust their interpretations and predictions accordingly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Liquid-type room-temperature fluoride ion batteries

The present disclosure relates to fluoride ion batteries and structures of metal based electrode materials for various fluoride ion batteries. The structures of the metal based electrode materials comprise one or more shells or interfaces, enabling the electrodes to operate at room temperature with a liquid electrolyte.

Xu, Qingmin↗
DOE OSTI2023

Mechanical Actuation via Homeomorphic Transformations of Topological Solitons within Polymer Coatings

Abstract Topological solitons are currently under investigation for their exotic properties, especially in nonlinear physics, optics, and material sciences. However, challenges of robust generation and limited stability over time have hindered their practical uses. To address this issue, an approach is developed to form structured arrays of solitons in films of polymerizable liquid crystals. Their complex molecular architecture is preserved by in situ photopolymerization forming a stable liquid crystal network. Most excitingly, their properties are advanced to include responsiveness functions. When thermally actuated, these topological solitons mediate the reconfiguration of surface topographies. Complex shape changes occur depending on the intrinsic complex spatial distribution of the director, which may even lead to full shape inversion and topographical changes as high as ≈40% of the initial thickness. Conversely, the shape changes provide information on the initial director profile, which is consistent with the mathematical model. The soliton‐containing polymer coatings are applicable in multiple domains, ranging from tunable optics to haptics, and from shape‐coupled sensing systems to temperature‐coupled heat management.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Direct Recycling of Spent NCM Cathodes through Ionothermal Lithiation

Ionic liquids (ILs) are a family of nonconventional molten salts that offer many advantages, such as negligible vapor pressures, negligible flammability, wide liquidus ranges, good thermal stability, and much synthesis flexibility. The unique solvation environment of these ILs provides new reaction or flux media for controlling formation of solid-state materials with a minimum perturbation of morphologies. A successful lithiation via ionothermal synthesis using a cost-effective Li halide as Li source and recyclable ILs as solvents is reported in this study for the direct recycling of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM 111) cathodes. In addition, the ionic liquids can be readily recycled and reused after ionothermal lithiation. The lithiation of spent cathodes can enable the direct recycling of spent cathode materials in lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Amphiphilic Heterografted Molecular Bottlebrushes with Tertiary Amine-Containing Side Chains as Efficient and Robust pH-Responsive Emulsifiers

Here, by combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli-responsive polymers, we show that MBBs with randomly grafted poly(n-butyl acrylate) and pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH-responsive emulsifiers. Water-in-toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water-insoluble, and the MBBs desorbed from the interface, causing de-emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗