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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Imide Oligomers Endcapped with Phenylethynl Phthalic Anhydrides and Polymers Therefrom

Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N.N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or cheznicauy to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydxide(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

Hergenrother, Paul M.↗
DOE OSTI2022

Not All Aggregates Are Made the Same: Distinct Structures of Solution Aggregates Drastically Modulate Assembly Pathways, Morphology, and Electronic Properties of Conjugated Polymers

Abstract Tuning structures of solution‐state aggregation and aggregation‐mediated assembly pathways of conjugated polymers is crucial for optimizing their solid‐state morphology and charge‐transport property. However, it remains challenging to unravel and control the exact structures of solution aggregates, let alone to modulate assembly pathways in a controlled fashion. Herein, aggregate structures of an isoindigo–bithiophene‐based polymer (PII‐2T) are modulated by tuning selectivity of the solvent toward the side chain versus the backbone, which leads to three distinct assembly pathways: direct crystallization from side‐chain‐associated amorphous aggregates, chiral liquid crystal (LC)‐mediated assembly from semicrystalline aggregates with side‐chain and backbone stacking, and random agglomeration from backbone‐stacked semicrystalline aggregates. Importantly, it is demonstrated that the amorphous solution aggregates, compared with semicrystalline ones, lead to significantly improved alignment and reduced paracrystalline disorder in the solid state due to direct crystallization during the meniscus‐guided coating process. Alignment quantified by the dichroic ratio is enhanced by up to 14‐fold, and the charge‐carrier mobility increases by a maximum of 20‐fold in films printed from amorphous aggregates compared to those from semicrystalline aggregates. This work shows that by tuning the precise structure of solution aggregates, the assembly pathways and the resulting thin‐film morphology and device properties can be drastically tuned.

36 MATERIALS SCIENCE↗
NASA NTRS1997

Phenylethynyl Phthalic Anhydride

Controlled molecular weight PhenylEthynyl Terminated Imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with PhenylEthynyl Phthalic Anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2pyrrolidinone or N N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

Hergenrother, Paul M.↗
NASA NTRS2002

Assembly of Colloidal Materials Using Bioadhesive Interactions

We have pursued the use of biological crosslinking molecules of several types to make colloidal materials at relatively low volume fraction of colloidal particles. The objective is to make binary alloys of colloidal particles, made of two different colloidal particles coated with complementary biological lock-and-key binding molecules, which assemble due to the biological specificity. The long-term goal is to use low affinity lock-and-key biological interactions, so that the can anneal to form crystalline states. We have used a variety of different surface chemistries in order to make colloidal materials. Our first system involved using selectin-carbohydrate (sialyl-Lewis) interactions; this chemistry is derived from immune system. This chemical interaction is of relatively low affinity, with timescales for dissociation of several seconds. Furthermore, the adhesion mediated by these molecules can be reversed by the chelation of calcium atoms; thus assembled structures can be disassembled reversibly. Our second system employed avidin-biotin chemistry. This well-studied system is of high affinity, and is generally irreversible on a laboratory time-scale. Thus, we would expect selectin-carbohydrate interactions at high molecular density and avidin-biotin interactions to give kinetically-trapped structures; however, at low densities, we would expect significant differences in the structure and dynamics of the two materials, owing to their very different release rates. We have also begun to use a third chemistry - DNA hybridization. By attaching single stranded DNA oligonucleotide chains to beads, we can drive the assembly of colloidal materials by hybridization of complementary DNA chains. It is well known that DNA adenosine-thymine (A-T) and guanine-cytosine (G-C) bases hybridize pairwise with a Gibbs free energy change of 1.7 kcal/mol per base; thus, the energy of the assembly can be modulated by altering the number of complementary bases in the DNA chains. Using these different crosslinking molecules, we have assembled colloidal materials from different-sized colloidal particles, A and B. In the first sets of experiment, we used high densities of adhesion molecules, and 0.96 micron (A) and 5.5 micron (B) diameter particles. The high density of adhesion molecules means that the structures are kinetically trapped in nonequilibrium configurations. The structure of the suspension can be varied by changing the number ratio of the two types of colloidal particles, NA and NB, where A is the smaller particle. With carbohydrate-selectin or avidin-biotin interactions, large NA/NB leads to the formation of colloidal micelles, with the large center B particle surrounded by many smaller A particles. As the ratio NA/NB decreases, the structures become more extended, approaching the formation of macro-Rouse polymers - extended linear chains where A beads are connected with intervening small B linkers.

Hammer, Daniel A.↗
NASA NTRS1996

Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom

Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

Hergenrother, Paul M.↗
DOE OSTI2023

Post Access Report: Initial testing of wave energy powered UV-C LED anti-biofouling system

In the experiment entitled “Initial Testing of Wave Energy Powered UV-C LED Anti-Biofouling System,” a UV-C LED was used to treat platinum-coated titanium coupons emulating CTD electrode material. An additional control set of coupons were exposed to seawater without the LED treatment. The experimental setup was deployed in seawater tanks at PNNL-Sequim’s Marine and Coastal Research Laboratory (MCRL) for the duration of six months. Tank seawater temperature data were collected for the duration of the experimental campaign. At two-month intervals triplicate sets of coupons were removed from both treatment and control test chambers and weighed to characterize biomass accumulation. After weighing, the coupons were photographed in initial condition, with a stain applied to highlight biofouling growth, and after rinsing off excess stain. These photographs were analyzed using PNNL’s Biofouling Growth Index (BGI) software and with a calculation of percentage dark pixels after conversion to grayscale. Additionally, at the final 6-month datapoint triplicate sets of control and test coupons were sent to PNNL-Richland’s Environmental Molecular Sciences Laboratory (EMSL) for scanning electron microscopy. All data organization and collection methods are described in further detail in the document “TEAMER_3newable_Data_Guide.pdf.” Biomass accumulation increased over time on both sets of coupons, and percent area biofouled demonstrated a similar trend. Analysis of the collected data resulted in the findings that treatment method has an impact on biofouling growth, though to a much less significant extent than time does. Additionally, qualitative findings included the presence of advanced life forms such as worms in the control test chamber, but not in the treated test chamber.

16 TIDAL AND WAVE POWER↗
DOE OSTI2023

Fundamentals of SrCoO 3-δ Based Oxygen Deficient Perovskites as Cathodes for Solid Oxide Fuel Cells

The local structure and oxygen stoichiometry in oxide systems have a profound impact on oxygen electrocatalysis encountered in metal-air batteries and solid oxide fuel cells (SOFCs). However, this knowledge is often obtained under conditions different from the real working conditions of the material, resulting in misinterpretation and misunderstanding. This PhD dissertation aims to obtain the structure and oxygen-stoichiometry information of a class of perovskite oxides under their real working conditions in solid oxide fuel cells. Several perovskite oxides were selected for the study: Sr 0.9 Y 0.1 CoO 3-δ (SYC10), Sr 0.9 Y 0.3 CoO 3-δ (SYC30), SrCo 0.9 Nb 0.1 O 3-δ (SCN10) and SrCo 0.9 Ta0.1O 3-δ (SCT10). The local crystal structure and oxygen stoichiometry of these materials were systematically characterized with in-situ neutron diffraction (ND). The oxygen stoichiometry was also measured by thermogravimetric analysis (TGA) and iodometric titration methods. To establish the correlation among structure, oxygen stoichiometry and oxygen reduction reaction (ORR) activity, high temperature electrochemical impedance spectroscopy, oxygen permeation and single cell testing were also performed. In chapter 2, SYC10 is described to have a more symmetrical structure and $V_o^{··}$ distribution, and higher $V_o^{··}$ concentration than SYC30. Molecular orbital energy analysis based on the local structure of the ORR-active Co1-polyhedra indicates SYC30 has a higher Fermi level relative to O-2p energy level in the active Co1-polyhedra, and thus a higher motional enthalpy for $V_o^{··}$ migration. However, the ORR activity of Y-doped SrCoO 3-δ (SCO) are found uncompetitive with other popular catalysts. In chapter 3 and 4, systematic structural studies are presented for Nb and Ta-doped SCO, namely SCN10 and SCT10, respectively. The methodology of unrevealing the structure-activity relationships in chapter 2 is also found applicable to SYC10, SCN10 and SCT10 as presented in chapter 5. The electrochemical tests indicate that SCT10 is the best catalyst due to its excellent thermal and electrochemical stability. In chapter 6, SCT10 is evaluated in a real solid oxide fuel cell in the form of nanoscaled SCT10 layer coating on the commercial (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ (LSCF). The bilayer structured cathode shows excellent properties of coarsening-resistant, Sr-segregation-free and high ORR-activity.

Yang, Tianrang↗
DOE OSTI2022

Synthesis and thermomechanical characteristics of zwitterionic poly(arylene ether sulfone) copolymers

Charge-containing polymeric materials have been widely studied for a range of applications. The fundamental relationships between the charge species, charge density, and the microscale morphology of charge-containing polymers are critical for defining the application in which they may be used. In this work, a series of thermoplastic poly(arylene ether sulfone) (PAES) copolymers with controllable sulfobetaine charge contents (0~100 mol%) and high molecular weights (Mw ~ 65 kDa) were prepared. All the zwitterionic PAESs synthesized showed thermal stability up to 250 °C. DSC and tensile tests showed a decreased T g and mechanical strength with the incorporation of increasing charge density, which suggests a plasticization effect by the charged group. Electron microscopy and X-ray scattering data confirmed the absence of microphase separation in the ion-containing random copolymer system, which corroborated with the observation of a single T g for all zwitterionic copolymers studied. Furthermore, the relative hydrophilicity of the samples was evaluated by water uptake measurements, which revealed that the water uptake of the zwitterionic PAESs can reach up to 64% for the 72 mol% zwitterion copolymer while the free-standing film in the wet state still maintains a Young's modulus of 185 MPa. Here, the thermoplastic charge-containing copolymers in this work demonstrated potential for applications such as coatings or water purification membranes, in which balancing hydrophilicity, processibility, and thermomechanical performance are important.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

High-Performance Polymers Having Low Melt Viscosities

High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties.

Jensen, Brian J.↗
NASA NTRS2007

Optical Characterization of Molecular Contaminant Films

A semi-empirical method of optical characterization of thin contaminant films on surfaces of optical components has been conceived. The method was originally intended for application to films that become photochemically deposited on such optical components as science windows, lenses, prisms, thinfilm radiators, and glass solar-cell covers aboard spacecraft and satellites in orbit. The method should also be applicable, with suitable modifications, to thin optical films (whether deposited deliberately or formed as contaminants) on optical components used on Earth in the computer microchip laser communications and thin-film industries. The method is expected to satisfy the need for a means of understanding and predicting the reductions in spectral transmittance caused by contaminant films and the consequent deterioration of performances of sensitive optical systems. After further development, this method could become part of the basis of a method of designing optical systems to minimize or compensate for the deleterious effects of contaminant films. In the original outer-space application, these deleterious effects are especially pronounced because after photochemical deposition, the films become darkened by further exposure to solar vacuum ultraviolet (VUV) radiation. In this method, thin contaminant films are theoretically modeled as thin optical films, characterized by known or assumed values of thickness, index of refraction, and absorption coefficient, that form on the outer surfaces of the original antireflection coating on affected optical components. The assumed values are adjusted as needed to make actual spectral transmittance values approximate observed ones as closely as possible and to correlate these values with amounts of VUV radiation to which the optical components have been exposed. In an initial study, the method was applied in correlating measured changes in transmittance of high-purity fused silica photochemically coated with silicone films of various measured thicknesses and exposed to various measured amounts of VUV radiation. In each case, it was found to be possible to select an index of refraction and absorption coefficient that made the ultraviolet, visible, and infrared transmittance changes predicted by the model match the corresponding measured transmittance changes almost exactly.

Visentine, James T.↗
DOE OSTI2024

Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts

The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.

Sarma, Prasad V↗
DOE OSTI2021

New sterically hindered polyvinylamine-containing membranes for CO 2 capture from flue gas

Amine-containing facilitated transport membranes can have both high permeability and selectivity due to the reversible reaction between CO 2 and amino groups for effective carbon capture from flue gas. In this study, we have developed an improved method for the synthesis of high-molecular-weight sterically hindered polyvinylamine (PVAm) as the new fixed-site carrier in thin-film composite membranes for CO 2 capture. Commercially available PVAm was N-monomethylated into poly-N-methyl-N-vinylamine (PVAm-CH 3 ) using the stepwise reductive amination with a highly polar fluorinated alcohol as the solvent to enhance the equilibrium shift to the formation of the imine intermediate. The method prevented over-alkylation, resulting in the increased yield of the target product. PVAm-CH 3 exhibited excellent CO 2 facilitation with a CO 2 permeability of 445.7 Barrer (1 Barrer = 3.349 x 10 –16 mol m m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 70.3, which are above the Robeson 2008 upper bound. The PVAm-CH 3 solution retained a sufficiently high viscosity after incorporating the aminoacid salt, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar), as the mobile carrier for the membrane coating on nanoporous polyethersulfone (PES) substrates without any penetration issues. The resultant thin-film composite PVAm-CH3/PZEA-Sar membrane with a thickness of approximately 170 nm exhibited a superior CO 2 performance of 1071 GPU (1 GPU = 3.349 x 10 –10 mol m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 183 at 57°C and a feed gas pressure of 111.64 kPa (1.5 psig). This PVAm-CH 3 /PZEA-Sar membrane surpassed the latest redefined 2019 CO 2 /N 2 upper bound and outperformed other polymer-based membranes. Density functional theory calculations also demonstrated that PVAm-CH 3 showed a stronger preference, relative to PVAm, toward the more efficient bicarbonate pathway. Thus, the steric hindrance effect of PVAm-CH 3 enhanced the solubility of CO 2 in the polymer matrix and resulted in the higher CO 2 permeance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Size-Selective Nanoporous Atomically Thin Graphene Separators for Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) are extensively researched for their high energy densities but are hindered by the lithium polysulfide (LiPS) shuttling effect, which results in poor cyclability. A popular mitigation strategy is separator modification, where a LiPS trapping material is slurry-coated onto a conventional microporous polypropylene (PP) separator. This additional mass and volume unfortunately compromise the overall energy density of the LSB. This study aims to take a separator modification approach that avoids this issue. Nanoporous atomically thin membranes (NATMs) made of graphene are gaining attention for their scalable synthesis, tunable pore size, and negligible pore length. Herein, we apply a well-characterized graphene NATM for reasons similar to those of a size-selective interlayer in LSBs. The tailored pore size of ∼0.7–1.0 nm and atomic thinness facilitate the passage of Li + (solvated ionic diameters ∼0.54–1.26 nm) and blockage of larger LiPS (solvated ionic diameters ∼0.81–1.69 nm) without adding significant impedances or mass. The sulfur confinement is confirmed through scanning electron microscopy and energy-dispersive X-ray spectroscopy elemental analysis of the Li anode. An LSB with a NATM@PP separator shows virtually no capacity loss over 150 cycles, demonstrating efficacy of size-selective molecular sieving using NATMs in LSBs.

battery separator↗
DOE OSTI2020

Ultra-efficient polymer binder for silicon anode in high-capacity lithium-ion batteries

As a highly promising anode material for high-capacity lithium-ion batteries (LIBs), the low electronic conductivity and large volume variation of silicon (Si) make the slurry-coating Si based electrode requiring high content of “inert” materials and suffering rapid capacity fading. In this work, a polyimine, synthesized via one-step condensation reaction, has been demonstrated as an ultra-efficient polymer binder that can resolve the above issues. The polyimine binder containing Si electrode delivers superior electrochemical performance: a delithiation specific capacity of 804.4 mAh g –1 with capacity retention of 82.4% after 1000 cycles at the current density of 2 A g –1 . The high efficiency of polyimine binder for Si electrode has also been demonstrated with ultrahigh weight ratio of “active” material to “inert” material (R A/I ). The electrode with 95 wt% of Si (95Si/Polyimine, R A/I = 19) reveals a reversible delithiation capacity of 2114 mAh g –1 (capacity retention ~ 80.4%) over 200 cycles at the current density of 400 mA g –1 . Even at the high current density of 2 A g –1 , a delithiation capacity of 1087.8 mAh g –1 after 500 cycles can be obtained. Molecular simulations and atomic force microscopy (AFM) indentation are utilized to investigate the ultra-efficiency of polyimine binder. With simple manufacturing process and ultra-efficient binder performance, the designed polyimine binder will be definitely meaningful in achieving low-cost and high-capacity LIBs with prolonged cycle life.

25 ENERGY STORAGE↗
DOE OSTI2021

Modifying Li + and Anion Diffusivities in Polyacetal Electrolytes: A Pulsed-Field-Gradient NMR Study of Ion Self-Diffusion

Polyacetal electrolytes have been demonstrated as promising alternatives to liquid electrolytes and poly(ethylene oxide) (PEO) for rechargeable lithium-ion batteries; however, the relationship between polymer structure and ion motion is difficult to characterize. Here, we study structure-property trends in ion diffusion with respect to polymer composition for a systematic series of five polyacetals with varying ratios of ethylene oxide (EO) to methylene oxide (MO) units, denoted as P(xEO-yMO), and PEO. We first use 7 Li and 19 F pulsed-field-gradient NMR spectroscopy to measure cation and anion self-diffusion, respectively, in polymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixtures. At 90 °C, we observe modest changes in Li + diffusivity across all polymer compositions, while anion (TFSI - ) self-diffusion coefficients decrease significantly with increasing MO content. At a given reduced temperature (T - T g ), all polyacetal electrolytes exhibit faster Li + self-diffusion than PEO. Intriguingly, P(EO-MO) and P(EO-2MO) also show slower TFSI - anion self-diffusion than PEO at a given reduced temperature. Molecular dynamics simulations reveal that shorter distances between acetal oxygen atoms (O-CH 2 -O) compared to ether oxygens (O-CH 2 -CH 2 -O) promote more diverse, often asymmetric, Li + coordination environments. Finally, Raman spectra reveal that anion-rich ion clusters in P(EO-MO) and P(EO-2MO) lead to decreased anion diffusivity, which along with increased cation diffusivity, support the viability of polyacetals as high-performance polymer electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Exploring rock-regolith interfaces in Jezero crater with Mars 2020 SHERLOC

The Perseverance rover successfully landed in Jezero crater, Mars in February 2021 at the Octavia E. Butler landing site and began its mission to explore and sample an ancient crater lake basin. Principal goals of the Mars 2020 mission include characterizing the geology of Mars and seeking signs of ancient microbial life via the spacecraft cameras and spectroscopic instruments onboard. The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument is a deep UV Raman spectrometer that utilizes a 248.6nm pulsed laser. Part of SHERLOC is a color camera known as the Wide Angle Topographic Sensor for Operations and eNgineering (WATSON). The SHERLOC suite provides coordinated, spectroscopic and imaging capabilities at high spatial resolution, to detect minerals and organic molecules in microtextural context. By pairing high spatial resolution (~100 μm) resonance Raman and native fluorescence spectroscopy with microscopic imaging in a novel spacecraft capability, SHERLOC enables texture-specific molecular composition measurements of rock and regolith targets on Mars. Coordinated rock-regolith observations illuminate unique insights into weathering processes and thereby to primary properties of rocks in Jezero crater. This work describes the potential of rock-regolith interfaces to preserve unique records of geological processes in Jezero crater and can powerfully supplement observations of the more general rock record on Mars. Linking observations of local rock texture with associated regolith reveals important lithologic information based on the interrelationship between differential weathering behavior and mineralogy, grain size, and cement chemistry. Preliminary observations indicate that the polygonally fractured lithotype common near the Octavia E. Butler landing site may weather by granular disintegration and/or surface creep, a relation that can be uniquely observed at the rock-regolith interface. SHERLOC -specific observations of microtextural and elemental composition transitions presented here trace rock-regolith boundaries at multiple indurated surfaces adjacent to regolith. At these locales, grain-scale based examinations suggest chemical weathering could be related to a variably distributed coating or rind on dark rock targets that may be mafic in composition. Granule deposits overlying widely distributed fine-grained material are also observable. Mineral identifications of each phase are presented, with cross-scale comparisons to the remote insights gained by the SuperCam instrument.

Emily L. Cardarelli↗
DOE OSTI2023

Kinetic Effects of Anion Clusters on the Interfacial Stability between Solid-State Electrolyte and Metal Anode

The success of all-solid-state batteries (ASSBs) depends on the solid-state electrolyte (SSE) exhibiting high interfacial stability and room-temperature ionic conductivity. However, the current SSEs, especially those with practical ionic conductivities (≥10 –3 S/cm) at room temperature, often develop unstable interfaces at the metal anode, in some cases with even greater severity than with liquid organic electrolytes. Despite persistent efforts, achieving interfacial stability and sufficient ionic conductivity simultaneously represents one of the greatest challenges in ASSBs. The current approaches focus on stabilizing the interface by incorporating secondary interlayers or introducing coatings by surface engineering. The method is often material-specific, and the added interlayers often deteriorate during cycling. In this work, using phase analysis and explicit interface modeling, we demonstrate a strategy to kinetically stabilize the interface between the SSE and metal anode by incorporating selected monoanion clusters in the SSE; they can effectively lower or even halt the reduction kinetics at the interface by promoting on-site formation of interphases that are highly electron insulating. The study provides insight into the kinetic effects to achieve SSEs with superior properties in bulk and at the interface.

25 ENERGY STORAGE↗
DOE OSTI2020

Effect of initial γ -irradiation on infrared laser ablation of poly(vinyl alcohol) studied by infrared spectroscopy

We report the effect of initial γ-irradiation of poly(vinyl alcohol) (PVA) on the kinetics of polymer ablation under CO 2 laser irradiation was studied using infra-red spectroscopy. The rate of laser ablation rapidly decreases with increasing time of laser ablation up to 10 s. Initial γ-irradiation of a dose up to 100 kGy reduces the rate of the laser ablation, just like the effect of laser exposure. The number of OH and CH groups decrease in PVA both with laser irradiation and with γ-irradiation. The number of OH groups decreases more under laser irradiation. Unsaturated bonds are formed in γ–irradiated PVA on the surface of the crater formed by laser ablation of the polymer that has undergone radiolysis. Increasing the dose of initial γ-irradiation from 100 to 2300 kGy leads to an increase in the intensity of the IR bands of the unsaturated bonds. The number of IR bands in the spectra of the laser ablation crater of PVA does not change with the dose of initial γ-irradiation. A dose of radiolysis of 3500 kGy significantly changes the IR spectra of both the ablation crater and the coating formed from the ablation products. Many bands characteristic for PVA are no longer present and the intensities of bands corresponding to unsaturated bonds are increased. A computational model for loss of water and ketone formation was developed for PVA and PVA including a diol using G3(MP2). The highest activation energy barrier step in the decomposition reaction was formation of the enol species and water was shown to catalyze all decomposition steps.

36 MATERIALS SCIENCE↗