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At least 37 records · Page 2

Chain extension epoxide polymerization to well‐defined block polymers using a N‐Al Lewis pair catalyst

Block polyethers comprised of poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEG or PEO) segments form the basis of ABA-type PEO-b-PPO-b-PEO poloxamer materials. The inverse architecture with an internal hydrophilic PEO segment flanked by hydrophobic blocks can be difficult to prepare with control of architecture by use of traditional anionic polymerization. These oxyanionic polymerizations are plagued by chain-transfer-to-monomer side reactions that occur with substituted epoxides such as propylene oxide (PO). Herein, we report a new method for the preparation of block polymers through a controlled polymerization involving a N-Al Lewis adduct catalyst and an aluminum alkoxide macroinitiator. The Lewis pair catalyst was able to chain-extend commercial PEO macroinitiators to prepare di-, tri-, and pentablock polyethers with low dispersity and reasonable monomer tolerance. Chain extension was confirmed using size exclusion chromatography and diffusion ordered nuclear magnetic resonance spectroscopy. In conclusion, the resulting block polymers were additionally analyzed with small-angle X-ray scattering to correlate the morphology to molecular architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Integrated Theoretical and Experimental Approach to Achieve Highly Polarizable Relaxor Ferroelectric Liquid Crystalline Polymers

In this project, we have designed and synthesized a series of aliphatic sulfonlyated chiral and achiral polyether. The major objective is to achieve ferroelectric liquid crystalline polymers with a high spontaneous polarization (0.04-0.08 C/m2). Due to the strong dipole-dipole interaction among the sulfonyl side groups, which resembles that among water molecules, these polyethers can exhibit various liquid crystalline self-assemblies without any rigid mesogens. By tuning the position of the sulfonyl groups, single versus double sulfonyl groups, and spacer/tail length and methyl branches, the liquid crystalline phases include smectic A, smectic C, and hexagonal columnar phases. When the single sulfonyl group is next to the main chain or disulfonyl groups are separated by a short C3 spacer, the dipolar interaction is too strong to allow any dipole switching. As a result, the linear dielectric behavior is observed with a low dielectric constant of 5-7. When the single sulfonyl groups are away from the main chain, the paraelectric behavior is obtained with a high dielectric constant around 20. From this study, we predict that by further tailoring the intermolecular interactions among the disulfonyl side groups, it is possible to achieve ferroelectric property for these liquid crystalline polymers. If successful, these ferroelectric liquid crystalline polymers can be used for efficient electrocaloric cooling applications.

36 MATERIALS SCIENCE↗

Molecular design and fabrication of PIM-1/polyphosphazene blend membranes with high performance for CO 2 /N 2 separation

New polymeric blend membranes for CO 2 separation were synthesized based on insights from molecular dynamics simulation. A molecular-level structure-property relationship in polymers of intrinsic microporosity (PIM) based blend membranes, was investigated in detail computationally. Calculated local density profiles and energy of interaction of the blend membranes, composed of PIM-1 and various polyphosphazenes, showed that using the polyphosphazene with a higher concentration of ether side chains can improve the compatibility with PIM-1. Furthermore, based on the findings of computational studies, blend membranes were experimentally fabricated from PIM-1 and polyphosphazenes with various polyether side chain concentrations. Polyether concentration in polyphosphazenes was correlated with the film properties and gas transport performance of the blend membranes. Blend membranes showed very high CO 2 permeability (3100-5300 barrer) and improved CO 2 /N 2 selectivity (24-28), outperforming all other PIM-based blend membranes reported to date. Moreover, the CO 2 permeability performance of the blend membranes was tested 566 hours under real post-combustion flue gas from a coal-fired power plant, including CO 2 , N 2 , H 2 O, O 2 , SO x and NO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyurethanes Based on Unmodified and Refined Technical Lignins: Correlation between Molecular Structure and Material Properties

The structural complexity and robust intermolecular interactions have challenged the incorporation of technical lignin into value-added polymeric materials for decades. To study the correlation between lignin molecular structure and material properties of lignin-based polyurethanes, we applied co-solvent enhanced lignocellulosic fractionation pretreatment followed by sequential precipitation to produce three distinct lignin preparations with narrowly distributed (molecular weight dispersity <2) and comparatively low molecular weight (<1500 g/mol) from poplar biomass. Structural characterization indicated that these lignin preparations differed in average molecular chain length and stiffness as well as hydroxyl group distribution. Secondary hydroxyl group providers such as aliphatic diols and polyethers were incorporated as building blocks into the lignin-based polyurethanes to provide additional hydrogen capacity to improve the dispersion of lignin in the polyurethane network. The selected aliphatic diols and polyethers interacted with lignin molecules at different levels of strength depending on their molecular structure, and their impacts were ultimately reflected in the mechanical and thermal properties of the resulting lignin-based polyurethanes. The copolymerization of technical lignin with tailored structure and secondary hydroxyl providers could provide new strategies in formulating lignin-based/containing polyurethanes for various functional applications.

36 MATERIALS SCIENCE↗

Molecular Dynamics and Free Energy Calculations of Dicyclohexano-18-crown-6 Diastereoisomers with Sm 2+ , Eu 2+ , Dy 2+ , Yb 2+ , Cf 2+ , and Three Halide Salts in Tetrahydrofuran and Acetonitrile Using the AMOEBA Force Field

With the continual development of lanthanides (Ln) in current technological devices, an efficient separation process is needed that can recover greater amounts of these rare elements. Dicyclohexano-18-crown-6(DCH18C6) is a crown ether that may be a promising candidate for Ln separation, but additional research is required. As such, molecular dynamics(MD) simulations have been performed on four divalent lanthanide halide salts(Sm 2+ , Eu 2+ , Dy 2+ , and Yb 2+ ) and one divalent actinide halide salt (Cf 2+ ) bound to three diastereoisomers of DCH18C6. Dy 2+ , Yb 2+ , Cf 2+ , DCH18C6, and tetrahydrofuran (THF) solvent were parameterized for the AMOEBA polarizable force field for the first time, whereas existing parameters for Sm 2+ and Eu 2+ were utilized from our previous efforts. A coordination number (CN) of six for Ln 2+ /An 2+ –O solvated in THF indicated that the cations interacted almost entirely with the oxygens of the polyether ring. A CN of one for Ln 2+ /An 2+ -N solvated in acetonitrile for systems containing iodide suggested that theN atom of acetonitrile was competitive with I – for cation interactions. Fluctuation between five and six CNs for Dy 2+ and Yb 2+ suggested that although the cations remained in the polyether ring, the size of the ring may not be an ideal fit as these cations possess comparatively smaller ionic radii. Gibbs binding free energies of Sm 2+ in all DCH18C6 diastereoisomers solvated in THF were calculated. The binding free energy of the cis-syn-cis diastereoisomer was the most favorable, followed by cis-anti-cis, and then trans-anti-trans. Lastly, two major types of conformation were observed for each diastereoisomer that were related to the electrostatic interactions and charge density of the cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Blending Polyurethane Thermosets Using Dynamic Urethane Exchange

Recycling crosslinked polyurethanes (PUs) is accomplished through mechanical or chemical processes that are energy-intensive or produce plastics of lesser value. Polymer recycling processes are notably intolerant of polymer mixtures, yet the ability to reprocess and compatibilize two or more crosslinked PUs together will make this process more amenable to mixed waste streams while offering an opportunity to tune the properties of the recycled polymer products. Here, we blend a rigid polyester PU and a soft polyether PU using twin-screw extrusion to yield materials with tunable mechanical properties based on the feed composition. Their material properties were compared to those of compression-molded reprocessed blends and blends where the monomers were mixed prior to synthesis. The extruded materials showed similar mechanical and thermal properties to newly prepared blends and had higher-value mechanical properties compared to the samples reprocessed via compression molding. The morphologies of the blends were observed using phase imaging via atomic force microscopy to show that there is less phase separation in the extruded materials compared to compression-molded blends. The mechanical properties of these materials were tunable from soft to elastomeric to rigid based on the feed composition, and this tunability was demonstrated through four consecutive reprocessing cycles, through which the mechanical properties were steadily varied from rigid to soft by incorporating increasing amounts of soft polyether PU material. Here, this blending method for reprocessing mixed waste compatibilizes different PUs and provides a means to tune the mechanical properties of a PU product, even if starting from waste streams of varying compositions. As such, this process represents an intriguing new approach for polymer reprocessing.

Extrusion↗

Robust Solid/Electrolyte Interphase (SEI) formation on Si Anodes Using Glyme-based Electrolytes

Silicon (Si) is the most naturally abundant element possessing 10-fold theoretical capacity than graphitebased anodes. The practicality of implementing Si anodes is, however limited by the unstable solidelectrolyte interphase (SEI) and anode fracturing during continuous lithiation/delithiation. We demonstrate that glyme-based electrolytes (GlyEls) assure a conformal SEI on Si and keep the Si ‘fracture-free’. Benchmarking against the optimal, commonly-used carbonate electrolyte with the fluoroethylene carbonate (FEC) additive, Si anode cycled in a GlyEl exhibits reduced early parasitic current (by 62.5%) and interfacial resistance (by 72.8%), while the cell capacity retention is promoted by >7% over a course of 110 cycles. The mechanistic investigation by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) indicates GlyEl enriches Si SEI with elastic polyether but diminishes its carbonate species. Glyme-based electrolytes prove viable in stabilizing the SEI on silicon for future high energy density lithium-ion batteries.

Yang, Guang↗

Catalytic strategy for conversion of fructose to organic dyes, polymers, and liquid fuels

We illustrate a process to produce a versatile platform chemical from biomass-derived fructose for organic dye, polymer, and liquid fuel industries. An aldol-condensed chemical (HAH) is synthesized as a platform chemical from fructose by catalytic reactions in acetone/water solvent with non-noble metal catalysts (e.g., HCl, NaOH). Then, selective reactions (e.g., etherification, reduction, dimerization) of the functional groups, such as enone and hydroxyl groups, in the HAH molecule enable applications in organic dyes and polyether precursors. High yields of target products, such as 5-(hydroxymethyl) furfural (HMF) (85.9% from fructose) and HAH (86.3% from HMF) are achieved by sequential dehydration and aldol-condensation with a simple purification process (>99% HAH purity). The use of non-noble metal catalysts, the high yield of each reaction, and the simple purification of the target product allow for beneficial economics of the process. Techno-economic analysis indicates that the process produces HAH at minimum selling price (MSP) of $1958 per ton. The MSP of HAH product allows the economic viability of applications in organic dye and polyether markets by replacing its counterparts, such as anthraquinone ($3200-$3900 per ton) and bisphenol-A ($1360-$1720 per ton).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding why poly(acrylic acid) works: decarbonylation and cross-linking provide an ionically conductive passivation layer in silicon anodes

Poly(acrylic acid) (PAA) is commonly used as a binder for fabricating silicon (Si) anode active materials in lithium-ion batteries due to its useful properties including high polar solvent solubility, good rheology, and strong adhesive properties. However, the role and evolution of PAA during electrode fabrication, cycling, and calendar aging are not well understood. In this work, we reveal the evolution of PAA during electrode curing and relate its chemical change to the final electrode properties and performance. These studies are made possible using two types of in situ attenuated total reflectance-infrared Fourier transform (ATR-FTIR) spectroscopy: thermal ATR-FTIR to probe the cross-linking reaction, and ATR-FTIR spectroelectrochemistry of three-dimensional composite electrodes, a unique technique developed herein that probes the solvation dynamics of lithium ions at the silicon anode interface under electrochemical polarization. Specifically, we show that PAA undergoes a thermally-mediated, cross-linking decarbonylation reaction to form an ether-based network polymer. To show the importance of the polyether moieties, we synthesize partially esterified PAA analogues that do not undergo this cross-linking decarbonylation reaction and correlate the degree of cross-linking to half-cell performance metrics. Finally, we unveil the mechanism of the polyether binder performance through in situ ATR-FTIR spectroelectrochemistry and show that PAA acts as an interfacial material that conducts lithium-ions, limits solvent molecule access to the Si surface, and stabilizes the electrode against parasitic lithium inventory loss at high state of charge for an extended period of time.

25 ENERGY STORAGE↗

Proton exchange membrane fuel cells

Disclosed embodiments concern a membrane electrode assembly or a proton exchange membrane fuel cell comprising a phosphoric acid-doped polymeric membrane comprising a cationic functional group, such as an assembly or fuel cell having an ion exchange capacity of 0.8 to 3 mmol/gram and an operating temperature range of from 80° C. to 220° C. The cationic functional group can be any suitable functional group, such as ammonium, imidazolium, guanidinium, phosphazenium, sulfonium, oxonium, and phosphonium, with working embodiments typically using quaternary ammonium cationic functional groups tethered to the polymeric core. The polymeric material may be any suitable polymeric material, such as a material selected from polyaryl polymers, polyarylamides, polyimides, polystyrenes, polysulfones, polyethers, polyether sulfones, polyketones, polyetherketones, polyarylethers, polyolefins, and polynitriles. The membrane electrode assembly or a proton exchange membrane fuel cell can be used in any application now known or hereafter developed, such as a vehicle or a stationary power device.

30 DIRECT ENERGY CONVERSION↗

Low-temperature selective laser sintering 3D printing of PEEK-Nylon blends: Impact of thermal post-processing on mechanical properties and thermal stability

Herein, a high-performance polymer (HPP) (polyether ether ketone, PEEK) blended with a commercial low-temperature polymer (polyamide 12, PA-12) was fabricated using a low-temperature selective laser sintering (SLS) 3D printer. Different post-processing heat treatments were implemented after fabrication to tune the thermal and mechanical properties of printed blends. The specific mechanical modulus of the blend was increased up to 79% in comparison to printed PA-12 samples with heat treatment. Additionally, the thermal resistance of the treated blends greatly exceeded the properties observed using PA-12 alone. This research proposes a methodology to fabricate and engineer HPP using desktop SLS printers through a secondary lower melting temperature material and heat treatments.

36 MATERIALS SCIENCE↗

Experimental and modeling studies of IPDI-based polyurea elastomers – The role of hard segment fraction

Segmented polyureas (PUa) are industrially important class of polymers widely used in coatings, sealant, and adhesive applications. Here, in this paper, we report synthesis, characterization, and modeling of Isophorone Diisocyanate-Diethyl-Toluene-Diamine-Polyether amine (IPDI-DETDA-PO PUa) with varied hard segment contents of 20, 30, and 40 weight percent. For each of the three materials, we study its structure and phase behavior using FTIR, DSC, and TEM, and clearly show the presence of microphase separation between the hard and soft nanodomains. We then measure the linear viscoelastic response of the PUa-s using DMA (frequency sweeps at multiple temperatures). The DMA data are shown to obey the time-temperature superposition. Finally, we develop a new micromechanical model describing the DMA results; the model describes a phase-separated PUa as two “Fractional-order Maxwell gels” branches, connected in parallel, with the first FMG branch representing the “percolated hard phase" and the second one modeling the “filled soft phase". In agreement with the earlier thermodynamic theories, the volume-fraction of the percolated hard phase is related to the hard segment weight-fraction (HSWF), defined as the combined mass of IPDI and DETDA normalized to the total mass of the polymer. The data and model are found to be in a good qualitative and quantitative agreement.

36 MATERIALS SCIENCE↗

Enhancing CO 2 Transport Across a PEEK‐Ionene Membrane and Water‐Lean Solvent Interface

Abstract Efficient direct air capture (DAC) of CO 2 will require strategies to deal with the relatively low concentration in the atmosphere. One such strategy is to employ the combination of a CO 2 ‐selective membrane coupled with a CO 2 capture solvent acting as a draw solution. Here, the interactions between a leading water‐lean carbon‐capture solvent, a polyether ether ketone (PEEK)‐ionene membrane, CO 2 , and combinations were probed using advanced NMR techniques coupled with advanced simulations. We identify the speciation and dynamics of the solvent, membrane, and CO 2 , presenting spectroscopic evidence of CO 2 diffusion through benzylic regions within the PEEK‐ionene membrane, not spaces in the ionic lattice as expected. Our results demonstrate that water‐lean capture solvents provide a thermodynamic and kinetic funnel to draw CO 2 from the air through the membrane and into the bulk solvent, thus enhancing the performance of the membrane. The reaction between the carbon‐capture solvent and CO 2 produces carbamic acid, disrupting interactions between the imidazolium (Im + ) cations and the bistriflimide anions within the PEEK‐ionene membrane, thereby creating structural changes through which CO 2 can diffuse more readily. Consequently, this restructuring results in CO 2 diffusion at the interface that is faster than CO 2 diffusion in the bulk carbon‐capture solvent.

Walter, Eric D.↗

Multiscale porosity characterization in additively manufactured polymer nanocomposites using micro-computed tomography

Extrusion-based additive manufacturing (AM) of polymer composites exhibits complex thermally driven phenomena that introduce severe discontinuities in the internal structure across length scales, especially voids or porosity. This study utilizes a high-throughput porosity characterization technique to analyze large datasets from numerous micro-computed tomography (mu CT) scans to capture the influence of AM print parameters on the size, shape, and location of porosity across multiple print layers (up to a few cm) on fused granular fabrication (FGF) printers. The materials investigated include nanocomposite formulations based on commercially relevant nylon-12 and polyether ketone ketone (PEKK) materials comprising nano- or micro- sized fillers. The estimated global porosity follows an inverse linear correlation against the bulk density of the printed samples. Increasing the extrusion multiplier (EM) and the nozzle temperature while decreasing the print speeds reduces the global porosity. Outlier analyses (local porosity morphology) show that faster print speeds and higher extrusion rates result in long, slender inter-layer voids, while lower nozzle temperatures lead to large, symmetrical, inter-bead voids (at the bead junction). Lack of active chamber temperature increases inter-layer and intra-bead voids with a two-fold increase in global porosity. Overall, the micro filler-reinforced composites exhibit higher global porosity than nanofiller-reinforced composites, which is attributed to the increased mismatch in the thermal expansion coefficient between the filler and the polymers used in the study.

36 MATERIALS SCIENCE↗

Copper(I) photosensitizer-silica nanoparticle assembly towards enhanced aqueous photoluminescence

Harnessing the luminescence potential of Cu(I) complexes in aqueous media is typically hindered by their poor photostability and altered properties. Here, we report the synthesis, engineering and morphological characterization of a hydrophobic homoleptic copper(I) complex entrapped into silica nanoparticles, Cu-I@SiO 2 (where “Cu-I” designates [Cu(2,9-diiodo-1,10-phenanthroline) 2 ] + ), as a promising stabilisation strategy towards water-compatible, Cu(I) complex-based luminescence. The polyether chain-decorated nano-objects are spherical with an average diameter of ca. 10.8 ± 1.9 nm. Upon dispersion in water, clear solution-like suspensions were obtained. Significantly, the aqueous suspensions photo-luminesce (Φ em = 5×10 -4 ) upon excitation through the Metal-to-Ligand Charge-Transfer transition (MLCT) of the embedded copper(I) complexes. In contrast, the corresponding silica-free molecular complex dissolved in an aqueous environment revealed fully quenched emission. Finally, the use of Cu-I@SiO 2 suspensions as luminescent probes is reported, first by assessing their potential use as electrochemiluminescent probes, and second by monitoring the photoluminescence from Cu-I@SiO 2 in the presence of whole blood.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial engineering for stabilizing polymer electrolytes with 4V cathodes in lithium metal batteries at elevated temperature

Poly (ethylene oxide) (PEO) polymer electrolytes are promising candidates for next-generation rechargeable lithium batteries. However, the poor interfacial stability between 4 V cathodes and PEO electrolytes impedes their applications in 4 V lithium batteries with high energy density. Here, we demonstrate a facile and effective strategy to enhance the interfacial stability by the synergy of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) coating on the cathode surface, and salt combination in the electrolyte, even with a cut-off voltage of 4.25–4.4 V vs. Li + /Li. Nano-LAGP coated Li|PEO|LiCoO 2 cell delivers stable cycling with a capacity retention of 81.9%/400 cycles and 84.7%/200 cycles at 60 °C when charged to 4.25 and 4.3 V in pure polyether electrolyte, respectively. Steady cycling is also demonstrated at room temperature and with LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) cathode. This work offers a viable and scalable approach to improve the stability between PEO electrolytes and 4 V cathodes and open up new possibilities for practical application of 4 V lithium metal batteries.

25 ENERGY STORAGE↗

Dynamic heterogeneity and nanophase separation in rubber-toughened amine-cured highly cross-linked polymer networks

Solid state nuclear magnetic resonance (NMR) spectroscopy and small-to wide-angle X-ray scattering (SWAXS) methods were used to characterize the heterogeneous dynamics and polymer domain structure in rubber modified thermoset materials containing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin and a mixture of Jeffamine reactive rubber and 4,4-diaminodicyclohexylmethane (PACM) amine curing agent. The polymer chain dynamics and morphologies as a function of the PACM/Jeffamine ratio were determined. Using dipolar-filtered NMR experiments, the resulting networks are shown to be composed of mobile and rigid regions that are separated on nanometer length scales, along with a dynamically immobilized interface region. Proton NMR spin diffusion experiments measured the dimensions of the mobile phase to range between 9 and 66 nm and varied with the relative PACM concentration. Solid state 13 C magic angle spinning NMR experiments show that the highly mobile phase is composed entirely of the dynamically flexible polyether chains of the Jeffamine rubber, the immobilized interface region is a mixture of DGEBA, PACM, and the Jeffamine rubber, with the PACM cross-linked to DGEBA predominantly residing in the rigid phase. The SWAXS results showed compositional nanophase separation spanning the 11–77 nm range. These measurements of the nanoscale compositional and dynamic heterogeneity provide molecular level insight into the very broad and controllable glass transition temperature distributions observed for these highly cross-linked polymer networks.

36 MATERIALS SCIENCE↗

Microextraction-Single Particle-Inductively Coupled Plasma-Mass Spectrometry for the Direct Analysis of Nanoparticles on Surfaces

A novel employment of single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) was developed, where a microextraction (ME) probe is used to sample nanoparticles from a surface and analyze them in a single analytical step. The effects of several parameters on the performance of ME-SP-ICP-MS were investigated, including the flow rate, choice of carrier solution, particle size, and the design of the microextraction probe head itself. The optimized ME-SP-ICP-MS technique was used to compare the extraction efficiency (EE, defined as the ratio of particles measured to particles deposited on the surface) of the commercial probe head to a newly designed SP polyether ether ketone (PEEK) probe head. The SP PEEK probe head was found to have increased EE compared to the commercial probe head (8.5 ± 3% vs 3.9 ± 3%, respectively). Increasing the carrier solution flow rate was found to decrease the total analysis time at the cost of decreasing EE. Extraction efficiencies for ME-SP-ICP-MS were typically 4–10%, which is similar to transport efficiencies (1–10%) for conventional SP-ICP-MS. Lastly, ME-SP-ICP-MS was employed for the analysis of nano- and microparticles. The sizes of gold nanoparticles, 30 ± 3 and 51 ± 1.9 nm (certified sizes), and iron-based microparticles, 1000 ± 50 nm (certified size), were accurately determined to be 32.2 ± 2.5, 50.8 ± 3.4, and 1030 ± 57 nm, respectively, by ME-SP-ICP-MS. Further, this work demonstrates the potential of ME-SP-ICP-MS for the direct analysis of particles on common collection surfaces (GSR tabs, carbon planchettes, etc.) while retaining spatial information on particle distribution across the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗