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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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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Growth of GaP1 − x − yAsyNx on Si substrates by chemical beam epitaxy

Chemical beam epitaxy has been used to grow layers of GaP1 − xNx, GaP1 − yAsy, and nearly lattice-matched layers GaP1 − x − yAsyNx on Si substrates. To address the issue of antiphase domain generation associated with the growth of polar semiconductors on Si, misoriented Si(001) substrates have been used combined with a carefully designed GaP buffer layer growth. The reflection high-energy electron diffraction pattern exhibits a (2 × 4) surface reconstruction after GaP buffer layer and GaP(As,N) graded layer growth, indicating the good surface quality and planarity of the grown layers. Sample composition was obtained by simultaneous acquisition of Rutherford backscattering spectrometry and nuclear reaction analysis, indicating a linear dependence of N and As mole fractions on the flux of their respective precursor. GaP1 − x − yAsyNx layers grown on Si substrates have a lattice mismatch not larger than ±0.005 for N contents in the range 0.02 < x < 0.05. High-resolution X-ray diffraction reciprocal space maps demonstrate a good crystalline quality. Intense photoluminescence spectra have been measured in all GaP1 − xNx and GaP1 − x − yAsyNx layers, as it is expected for direct bandgap materials. Two wide overlapped emission peaks are observed in all the spectra, most likely related to near bandgap recombination. The position of the higher energy peak for GaP1 − xNx and GaP1 − x − yAsyNx layers has been compared to bandgap energy calculations using the band anticrossing model, showing good agreement.

Ben Saddik, K.↗
DOE OSTI2023

Electric Vehicle Lithium-Ion Battery Life Cycle Management

There is no question that electric vehicles (EVs), which are key for addressing climate change impacts from the transportation sector, are quickly gaining popularity and availability. With limits and other challenges related to the supply of critical battery minerals, maximizing the use of EV batteries and ensuring recovery of battery minerals is imperative. Therefore, proper end-of-life-cycle management (reuse and recycling) of these batteries must be part of the EV ecosystem from the perspective of both the supply chain and environmental footprint. Second use of batteries for energy storage systems extends the initial life of these resources and provides a buffer until economical material recovery facilities are in place. Although there are multiple pathways to recycling and recovery of materials, new recovery technologies are moving toward commercially available hydrometallurgy and promising direct recycling, which analysis has shown has the lowest overall carbon footprint. Strategically locating these plants close to battery collection further reduces transportation and thus recycling and recovering costs. Proper life cycle management could alleviate future lithium-ion battery materials supply chains for EVs. Governments and other stakeholders around the world have started initiatives and proposed regulations to address the challenges associated with life cycle management of EV lithium batteries. Finally, as manufacturers are increasingly faced with the likelihood of such extensive regulatory requirements, attention should be given to new designs, sales, and service models that can reduce life cycle management costs.

25 ENERGY STORAGE↗
DOE OSTI2018

Buffer Material Degradation in High Level Radioactive Waste Disposal - 18454

The concept of geological disposal for high-level radioactive waste (HLW) is based on a multi-barrier system comprising the natural geological barrier that repository host rock provides and its surroundings, as well as an engineered barrier system (EBS) that includes waste form, waste canisters, buffer materials, and backfill. The multi-barrier system is expected to perform its desired functions to isolate waste from the biosphere and achieve HLW disposal. Because of the interaction processes of radionuclide decay heat with hydraulic and water-mineral reactions in the radioactive waste repository, the bentonite buffer degradation resulting from the external temperature and pressure warrants investigation. However, seldom addressed in Taiwan is the influence of thermo-hydro-chemical (T-H-C) processes on buffer material degradation in the EBS of HLW disposal repositories as related to smectite clay dehydration. Therefore, we adopted the chemical kinetic model of smectite dehydration to calculate the amount of water expelled from smectite clay minerals caused by higher temperatures of waste decay heat. We discovered that smectite clay could cause volume shrinkage because of a loss of interlayer water, which can lead to bentonite buffer compression. The results of this study may be used in advanced research on the evolution of bentonite degradation for both performance assessments and safety analyses of final HLW disposal in Taiwan. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Enhancing the electron mobility in Si-doped (010) β-Ga 2 O 3 films with low-temperature buffer layers

We demonstrate a new substrate cleaning and buffer growth scheme in β-Ga 2 O 3 epitaxial thin films using metal–organic vapor phase epitaxy (MOVPE). For the channel structure, a low-temperature (LT, 600 °C) un-doped Ga 2 O 3 buffer was grown, followed by a transition layer to a high-temperature (HT, 810 °C) Si-doped Ga 2 O 3 channel layers without growth interruption. The (010) Ga 2 O 3 Fe-doped substrate cleaning uses solvent cleaning, followed by additional hydrofluoric acid (49% in water) treatment for 30 min before the epilayer growth. This step is shown to compensate the parasitic Si channel at the epilayer–substrate interface that originates from the substrate polishing process or contamination from the ambient. From secondary ion mass spectroscopy (SIMS) analysis, the Si peak atomic density at the substrate interface is found to be several times lower than the Fe atomic density in the substrate—indicating full compensation. The elimination of the parasitic electron channel at the epi–substrate interface was also verified by electrical (capacitance–voltage profiling) measurements. In the LT-grown (600 °C) buffer layers, it is seen that the Fe forward decay tail from the substrate is very sharp, with a decay rate of ∼9 nm/dec. X-ray off-axis rocking curve ω-scans show very narrow full width at half maximum (FWHM) values, similar to the as-received substrates. These channels show record high electron mobility in the range of 196–85 cm 2 /V⋅s in unintentionally doped and Si-doped films in the doping range of 2 × 10 16 –1 × 10 20 cm −3 . Si delta-doped channels were also grown utilizing this substrate cleaning and the hybrid LT buffers. Record high electron Hall mobility of 110 cm 2 /V⋅s was measured for sheet charge density of 9.2 × 10 12 cm −2 . This substrate cleaning, combined with the LT buffer scheme, shows the potential of designing Si-doped β-Ga 2 O 3 channels with exceptional transport properties for high-performance Ga 2 O 3 -based electron devices.

Bhattacharyya, Arkka↗
DOE OSTI2015

PLZT Film Capacitors for Power Electronics and Energy Storage Applications

Ceramic film capacitors with high dielectric constant and high breakdown strength hold special promise for applications demanding high power density. By means of chemical solution deposition, we deposited ≈2-μm-thick films of lanthanum-doped lead zirconate titanate (PLZT) on LaNiO3-buffered Ni (LNO/Ni) foils and platinized silicon (PtSi) substrates. The dielectric properties and energy storage performance of the resulting samples were determined under a high level of applied electric field. X-ray diffraction stress analysis revealed that PLZT on LNO/Ni bears a compressive stress of ≈370 MPa while PLZT on PtSi endures a tensile stress of ≈250 MPa. Compressive stress was found to lead to heightened polarization, improved tunability, increased irreversible domain wall motion, and enhanced breakdown strength for PLZT deposited on the LNO/Ni as compared with the PtSi substrate. We observed a tunability of ≈55 and ≈40 % at room temperature under 100 kV/cm applied field, remanent polarization of ≈23.5 and ≈7.4 µC/cm^2, coercive electric field of ≈25.6 and ≈21.1 kV/cm, and dielectric breakdown strength of ≈2.6 and ≈1.5 MV/cm for PLZT deposited on LNO/Ni foils and PtSi substrates, respectively. A high recoverable energy density of ≈85 J/cm^3 and energy conversion efficiency of ≈65 % were measured on the PLZT film grown on LNO/Ni.

ceramic film capacitor↗
DOE OSTI2017

Transplantation of dedifferentiation fat cells promotes intervertebral disc regeneration in a rat intervertebral disc degeneration model

Our group has reported that mature adipocyte-derived dedifferentiated fat (DFAT) cells show multilineage differentiation potential similar to that observed in mesenchymal stem cells. In the present study, we examined whether DFAT cell transplantation could contribute to intervertebral disc regeneration using a rat intervertebral disc degeneration (IDD) model. The IDD was created in Sprague-Dawley rats by puncturing at level of caudal intervertebral disc under fluoroscopy. One week after injury, rat DFAT cells (5 × 10{sup 4}, DFAT group, n = 13) or phosphate-buffered saline (PBS, control group, n = 13) were injected into the intervertebral disc. Percent disc height index (%DHI) was measured every week and histology of injured disc was evaluated at 8 weeks after transplantation. Radiographic analysis revealed that the %DHI in the DFAT group significantly higher than that in the control group at 2–3 weeks after transplantation. Histological analysis revealed that ectopic formation of nucleus pulposus (NP)-like tissue at the outer layer of annulus fibrosus was frequently observed in the DFAT group but not in the control group. Transplantation experiments using green fluorescent protein (GFP)-labeled DFAT cells revealed that the ectopic NP-like tissue was positive for GFP, suggesting direct differentiation of DFAT cells into NP-like cells. In conclusion, DFAT cell transplantation promoted the regeneration of intervertebral disc and improved intervertebral disc height in the rat IDD model. Because adipose tissue is abundant and easily accessible, DFAT cell transplantation may be an attractive therapeutic strategy against IDD. - Highlights: • Dedifferentiated fat cells (DFATs) are adipocyte-derived mesenchymal stem-like cells. • DFAT injection increases disc height in a rat intervertebral disc degeneration model. • Transplanted DFATs directly differentiate into the nucleus pulposus-like tissue. • DFATs may be an attractive cell source for intervertebral disc degeneration.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Contribution of capillary electrophoresis to an integrated vision of humic substances size and charge characterizations

The physicochemical properties of three different humic substances (HS) are probed using capillary zone electrophoresis in alkaline carbonate buffers, pH 10. Special attention is drawn to the impact of the electrolyte ionic strength and counter-ion nature, chosen within the alkali-metal series, on HS electrophoretic mobility. Taylor-Aris dispersion analysis provides insights into the hydrodynamic radius (R-H) distributions of HS. The smallest characterized entities are of nano-metric dimensions, showing neither ionic strength- nor alkali-metal-induced aggregation. These results are compared with the entities evidenced in dynamic light scattering measurements, the size of which is two order of magnitude higher, ca. 100 nm. The extended Onsager model provides a reasonable description of measured electrophoretic mobilities in the ionic strength range 1-50 mM, thus allowing the estimation of limiting mobilities and ionic charge numbers for the different HS samples. An unexpected HS electrophoretic mobility increase (in absolute value) is observed in the order Li{sup +} ≤ Na{sup +} ≤ K{sup +} ≤ Cs{sup +} and discussed either in terms of retarding forces or in terms of ion-ion interactions. (authors)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Heterostructures of metamorphic GaInAs photovoltaic converters fabricated by MOCVD on GaAs substrates

Heterostructures of metamorphic GaInAs photovoltaic converters (PVCs) are on GaAs substrates by the metal-organic chemical vapor deposition (MOCVD) method. It is shown that using a multilayer metamorphic buffer with a step of 2.5% in indium content and layer thicknesses of 120 nm provides the high quality of bulk layers subsequently grown on the buffer up to an indium content of 24%. PVCs with a long-wavelength photosensitivity edge up to 1300 nm and a quantum efficiency of ~80% in the spectral range 1050–1100 nm are fabricated. Analysis of the open-circuit voltage of the PVCs and diffusion lengths of minority carriers in the layers demonstrates that the density of misfit dislocations penetrating into the bulk layers increases at an indium content exceeding 10%.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Machine learning enhanced characterization and optimization of photonic cured MAPbI 3 for efficient perovskite solar cells

Photonic curing (PC) can facilitate high-speed perovskite solar cell (PSC) manufacturing because it uses high-intensity light pulses to crystallize perovskite films in milliseconds. However, optimizing PC conditions is challenging due to its many variables, and using power conversion efficiency (PCE) as the optimization metric is both time-consuming and labor-intensive. This work presents a machine learning (ML) approach to optimize PC conditions for fabricating methylammonium lead iodide (MAPbI 3 ) films by quantitatively comparing their ultraviolet-visible (UV-vis) absorbance spectra to thermal annealed (TA) films using four similarity metrics. We perform Bayesian optimization coupled with Gaussian process regression (BO-GP) to minimize the similarity metrics. Refining PC conditions using active learning based on BO-GP models, we achieve a PC MAPbI3 film with an absorbance spectrum closely matching a TA reference film, which is further verified by its crystalline and morphological properties. Thus, we demonstrate that the UV-vis absorption spectrum can accurately proxy film quality. Additionally, we use an AI-based segmentation model for a more efficient grain size analysis. However, when we use the optimized PC condition to fabricate PSCs, we find that interaction between MAPbI 3 and the hole transport layer (HTL) during PC critically degrades the PSC performance. By adding a buffer layer between the HTL and MAPbI 3 , the optimized PC PSCs produce a champion PCE of 11.8%, comparable to the TA reference of 11.7%. Using UV-vis similarity metrics instead of device PCE as the objective in our BO-GP method accelerates the optimization of PC processing conditions for MAPbI 3 films.

14 SOLAR ENERGY↗
DOE OSTI2019

Techno-Economic Analysis of Alternative Aqueous Phase Treatment Methods for Microalgae Hydrothermal Liquefaction and Biocrude Upgrading System

An economic analysis was conducted for an algae hydrothermal liquefaction (HTL) and biocrude upgrading system with alternative aqueous phase treatment methods. Using experimental data, three different methods were modeled and compared: 1) direct recycle HTL aqueous phase to the algae farm, 2) catalytic hydrothermal gasification (CHG), and 3) anaerobic digestion (AD). Direct recycle consumes the most natural gas because unlike AD and CHG, no methane is generated from the aqueous phase organics. However, direct recycle has the lowest cost compared to other two cases because it only requires the addition of pumps and buffer tankage related to aqueous phase recycle. The CHG and AD cases require significant capital and operating costs, which increase the minimum fuel selling price (MFSP) over the direct recycle case by 11% and 2.9%, respectively. CHG and AD respectively increase the conversion cost (excludes the cost to grow, harvest, and dewater algae) by 75% and 21%. Sensitivity analysis suggests that the key factors affecting the total cost of fuel production are the feedstock cost, biocrude yields, the plant scale, and the method of aqueous phase treatment.

Zhu, Yunhua↗
DOE OSTI2017

Coupled THMC models for bentonite in an argillite repository for nuclear waste: Illitization and its effect on swelling stress under high temperature

Subsurface manipulations such as those expected from the disposal of heat-emanating radioactive waste in deep repositories can induce strongly coupled Thermal (T), hydrological (H), mechanical (M) and chemical (C) processes. Adequate coupled THMC models are highly desirable or even indispensable for performance assessment of such repositories, for examples for the analysis of bentonite-based engineered barrier system (EBS) surrounding the emplaced waste. In this study, we present coupled THMC model simulations of a generic nuclear waste repository in an argillite with a bentonite-based buffer. The objective is to evaluate the chemical changes in the EBS bentonite and their effect on mechanical behavior under high temperature, attempting to shed light on whether EBS bentonite can sustain temperatures higher than 100 °C without significant impact on barrier's performance. Two scenarios were simulated for comparison: a case in which the temperature near the waste canister peaks at 200 °C and a case in which the temperature at the same spot culminate with about 100 °C. Simulations for a generic case with Kunigel-VI bentonite as backfill and Opalinus Clay as host rock were conducted for 1000 years and reported in the previous study (Zheng et al., 2015). In this paper, simulations for 100,000 years have been done for two types of bentonite-based buffer materials: Kunigel-VI and FEBEX bentonite. This enables us to evaluate how different types of bentonite behave in terms of the illitization and its impact on swelling stress and whether we can generalize these results to support decision making. The simulations show the occurrence of illitization in the bentonite buffer and the enhancement of illitization under high temperature. However, FEBEX bentonite undergoes less illitization mainly due to the higher ion concentration in pore water and the lower content of K-feldspar in the bentonite mineral composition. Moreover, the reduction of swelling stress by chemical changes is more pronounced for Kunigel-VI bentonite than for FEBEX bentonite. Furthermore, the results of our model simulations suggest that an argillite repository with a bentonite-based EBS that is similar to FEBEX bentonite could sustain temperatures much higher than 100 °C as far as illitization concerns. Model results also reveal that illitization is stabilized after about 2000 years in bentonite near the waste package, but continues in bentonite near the bentonite-argillite interface, which manifests the strong effect of geochemical interaction between EBS bentonite and host rock on long term illitization in bentonite.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Method for measurement of TRISO kernel and layer volumes by X-ray computed tomography

Layer dimensions are key parameters for as-fabricated tristructural-isotropic (TRISO) particle fuel as well as for post-irradiation examination of particle performance. Layer thicknesses are typically measured by optical microscopy of the particle cross section near mid-plane, while layer volumes are estimated with serial sectioning and microscopy. This method for measuring layer volumes is limited due to the resolution limit imposed by slice thickness and the effect of the polishing process on delicate irradiated particle microstructures. In this study, image processing software has been developed to segregate the three-dimensional (3D) TRISO particle images provided by x-ray computed tomography (XCT) into high-resolution volumetric data for the kernel, all particle layers, and any internal voids introduced during irradiation. These data can be used to analyze key in-reactor behaviors of TRISO particles such as kernel swelling or buffer shrinkage, which are important inputs for fuel performance modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The Effect of Acetylation on the Hydrolytic Degradation of PLA/Clay Nanocomposites

In this study, the hydrolytic degradation of Poly(lactic acid) (PLA) and acetylated PLA (PLA-Ac)–clay nanocomposites were investigated. The organo clay was obtained by ion exchange reaction using cetyl tri methyl ammonium bromide (CTAB). Nanocomposites containing 2, 5 and 8% mass ratio of organo clay (CTAB-O) were prepared. PLA and its organo clay nanocomposites were characterized by scanning electron microscope (SEM), thermo gravimetric analysis (TGA) and X-ray diffraction (XRD) to determine the morphology before and after hydrolytic degradation. Fourier transform infrared (FTIR) analyses of PLA and PLA-Ac were also obtained. The hydrolytic degradation of polymers and their composites were investigated in the phosphate buffered saline solution (PBS). The results showed that controlled hydrolytic degradation was observed in the samples with end group modification of PLA. While weight loss of PLA films was 28%, that of PLA-Ac films was 18% after 60 days degradation time. The weight loss was obtained as 29.5 and 25.5% for PLA-5 wt% organo clay (PLA/5CTAB-O) and PLA-Ac-5 wt% organo clay (PLA-Ac/5CTAB-O) nanocomposites films, respectively. It was also observed that thermal degradation of PLA-Ac was much more than that of PLA. Hydrolytic degradation increased depending on organo clay content. The end group modificated PLA results in controlled hydrolytic degradation. While hydrolytic degradation in polymer films occurred as surface erosion, bulk erosion was observed in composite films.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

The p-ERK–p-c-Jun–cyclinD1 pathway is involved in proliferation of smooth muscle cells after exposure to cigarette smoke extract

Highlights: • Smooth muscle cells proliferated after exposure to cigarette smoke extract. • The p-ERK, p-c-Jun, and cyclinD1 expressions increased in the process. • The p-ERK inhibitor, U0126, can reverse these effects. • The p-ERK → p-c-Jun → cyclinD1 pathway is involved in the process. - Abstract: An epidemiological survey has shown that smoking is closely related to atherosclerosis, in which excessive proliferation of vascular smooth muscle cells (SMCs) plays a key role. To investigate the mechanism underlying this unusual smoking-induced proliferation, cigarette smoke extract (CSE), prepared as smoke-bubbled phosphate-buffered saline (PBS), was used to induce effects mimicking those exerted by smoking on SMCs. As assessed by Cell Counting Kit-8 detection (an improved MTT assay), SMC viability increased significantly after exposure to CSE. Western blot analysis demonstrated that p-ERK, p-c-Jun, and cyclinD1 expression increased. When p-ERK was inhibited using U0126 (inhibitor of p-ERK), cell viability decreased and the expression of p-c-Jun and cyclinD1 was reduced accordingly, suggesting that p-ERK functions upstream of p-c-Jun and cyclinD1. When a c-Jun over-expression plasmid was transfected into SMCs, the level of cyclinD1 in these cells increased. Moreover, when c-Jun was knocked down by siRNA, cyclinD1 levels decreased. In conclusion, our findings indicate that the p-ERK–p-c-Jun–cyclinD1 pathway is involved in the excessive proliferation of SMCs exposed to CSE.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Functionalized Metal–Organic Framework Thin Films for Stable and Efficient Electrochemical Water Oxidation under Near-Neutral Conditions

The development of molecularly modified metal− organic frameworks (MOFs) for electrochemical water oxidation has emerged as a promising strategy for efficient artificial photosynthesis. In this study, a ruthenium-based water oxidation catalyst (WOC) was incorporated into the UiO-67 framework, forming RuM−UiO-67 films grown directly on conductive FTO substrates. These modified films demonstrate efficient water oxidation activity at near-neutral pH (pH 6), operating at a low overpotential of ∼600 mV. The catalyst exhibits a turnover frequency (TOF) of (0.32 ± 0.02) s −1 at 1.5 V versus the normal hydrogen electrode (NHE) in buffered solution (pH 6) for the oxygen evolution reaction. Notably, incorporation into the MOF results in a 12-fold increase in electroactive surface coverage compared to a monolayer of the same catalyst on bare FTO. Faradaic efficiency analysis revealed incomplete conversion to O 2 , and follow-up iodometric analysis confirmed the formation of H 2 O 2 as a competing two-electron oxidation product during electrocatalysis. These results highlight the utility of MOF-based architectures for maximizing the catalyst accessibility and stability under electrochemical water oxidation conditions.

catalysts↗
DOE OSTI2024

Trade can buffer climate-induced risks and volatilities in crop supply

Climate change is intensifying the frequency and severity of extreme events, posing challenges to food security. Corn, a staple crop for billions, is particularly vulnerable to heat stress, a primary driver of yield variability. While many studies have examined climate impact on average corn yields, little attention has been given to the climate impact on production volatility. This study investigates the future volatility and risks associated with global corn supply under climate change, evaluating the potential benefits of two key adaptation strategies: irrigation and market integration. A statistical model is employed to estimate corn yield response to heat stress and utilize NEX-GDDP-CMIP6 climate data to project future production volatility and risks of substantial yield losses. Three metrics are introduced to quantify these risks: Sigma (σ), the standard deviation of year-on-year yield change, which reflects overall yield volatility; Rho (ρ), the risk of substantial loss, defined as the probability of yield falling below a critical threshold; and Beta (β), a relative risk coefficient that captures the volatility of a region's corn production compared to the globally integrated market. The analysis reveals a concerning trend of increasing year-on-year yield volatility (σ) across most regions and climate models. This volatility increase is significant for key corn-producing regions like Brazil and the United States. While irrigated corn production exhibits a smaller rise in volatility, suggesting irrigation as a potential buffer against climate change impacts, it is not a sustainable option as it can cause groundwater depletion. On the other hand, global market integration reduces overall volatility and market risks significantly with less sustainability concerns. Furthermore, these findings highlight the importance of a multidimensional approach to adaptation in the food sector. While irrigation can benefit individual farmers, promoting global market integration offers a broader solution for fostering resilience and sustainability across the entire food system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2019

Multi-stimuli responsive tetra-PPO 60 -PEO 20 ethylene diamine block copolymer enables pH, temperature, and solvent regulation of Au nanoparticle composite plasmonic response

In this work a gold nanoparticle (NP) hydrogel composite prepared by multi-step cascade synthesis undergoes temperature, pH, and solvent dependent nanoscale structural transformations promoting modulation of the plasmon resonance. The composite is spontaneously prepared from a non-covalent lamellar structured lyotropic mesophase (complex fluid) composed of amphiphiles (DMPC and Triton X-100) that support the reactive constituents, a mixture of hydroxyl and acrylate end-derivatized Tetronic (Poloxamine) polymer and [AuCl4] – . The reaction sequence begins with the reduction of [AuCl4] – by the ethylene diamine linkage and PEO blocks of the Tetronic, yielding Au NPs. The redox reaction generates free radicals initiating crosslinking of the acrylate end-derivatized polymer producing a chemical hydrogel. Optical spectroscopy and electron microscopy confirm Au NP formation. ATR/FT-IR spectroscopy and thermal analysis establish acrylate crosslinking and network formation. X-ray scattering reveals the composite reversibly converts between multilamellar and bicontinuous cubic structures as temperature is increased above 35 °C for composites containing protonated ethylene diamine linkages (un-buffered water or acidic buffer). The reversible changes in nanoarchitecture red shifts and broadens the collective plasmon (from 523 nm to 575 nm) of the composite, an observation attributed to re-organization of confined NPs from 2D sheets (lamellae) to 1D columns (bicontinuous cubic channels). Composites prepared in alkaline buffer do not undergo a structural conversion with temperature, retaining a multilamellar architecture. In addition to pH and thermo-responsivity, the composite swells reversibly in polar solvents, which acts to de-aggregate and aggregate the encapsulated NPs and varies the plasmon resonance by Δ52 nm. This work reports the first combined use of a polymer to achieve both the in situ synthesis of spatially confined plasmonic NPs and their reversible stimuli-triggered re-organization mediated by interconvertible changes in scaffold nanoarchitecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Design of closed-loop recycling production of a Diels–Alder polymer from a biomass-derived difuran as a functional additive for polyurethanes

Acetalization of biomass-derived 5-hydroxymethyl furfural (HMF) with pentaerythritol produced a difuran (HPH) monomer in the presence of an acid catalyst. A recyclable polymer was then synthesized by Diels–Alder reaction of bismaleimide and the HMF-derived difuran (HPH). A polyurethane, produced from the Diels–Alder polymer has a higher glass transition temperature than a polyurethane, produced from ethylene glycol. The polyurethane, containing Diels–Alder polymer also has a self-healing ability. The Diels–Alder polymer could be hydrolyzed in acidic acetate buffer at 60 °C to produce the monomers for recycling. Each produced monomer was separated by solvent extraction, and the extracted monomers were recovered in different solvent fractions, such as aqueous, ethyl acetate, and acetone fractions. Techno economic analysis was used to assess the minimum selling price ($\$14.1$ per kg) for the primary production of Diels–Alder polymer at a feed capacity of 400 tons per year. The economic viability of the primary recovery process for the most expensive recovered monomer, bismaleimide, was assessed by calculating the minimum selling price of the bismaleimide ($\$15.2$ per kg). In conclusion, a circular closed-loop recycling production process for the Diels–Alder polymer was developed and this approach can produce the Diels–Alder polymer at $8.2 per kg when the feed capacity was 40 ktons per year.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗