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At least 253 records · Page 14

Revisiting Turbulence Model Validation for High-Mach Number Axisymmetric Compression Corner Flows

Two axisymmetric shock-wave/boundary-layer interaction (SWBLI) cases are used to benchmark one- and two-equation Reynolds-averaged Navier-Stokes (RANS) turbulence models. This validation exercise was executed in the philosophy of the NASA Turbulence Modeling Resource and the AIAA Turbulence Model Benchmarking Working Group. Both SWBLI cases are from the experiments of Kussoy and Horstman for axisymmetric compression corner geometries with SWBLI inducing flares of 20 and 30 degrees, respectively. The freestream Mach number was approximately 7. The RANS closures examined are the Spalart-Allmaras one-equation model and the Menter family of kappa − omega two equation models including the Baseline and Shear Stress Transport formulations. The Wind-US and CFL3D RANS solvers are employed to simulate the SWBLI cases. Comparisons of RANS solutions to experimental data are made for a boundary layer survey plane just upstream of the SWBLI region. In the SWBLI region, comparisons of surface pressure and heat transfer are made. The effects of inflow modeling strategy, grid resolution, grid orthogonality, turbulent Prandtl number, and code-to-code variations are also addressed.

Shock Wave↗

Evaluation of Industry Standard Turbulence Models on an Axisymmetric Supersonic Compression Corner

Reynolds-averaged Navier-Stokes computations of a shock-wave/boundary-layer interaction (SWBLI) created by a Mach 2.85 flow over an axisymmetric 30-degree compression corner were carried out. The objectives were to evaluate four turbulence models commonly used in industry, for SWBLIs, and to evaluate the suitability of this test case for use in further turbulence model benchmarking. The Spalart-Allmaras model, Menter's Baseline and Shear Stress Transport models, and a low-Reynolds number k- model were evaluated. Results indicate that the models do not accurately predict the separation location; with the SST model predicting the separation onset too early and the other models predicting the onset too late. Overall the Spalart-Allmaras model did the best job in matching the experimental data. However there is significant room for improvement, most notably in the prediction of the turbulent shear stress. Density data showed that the simulations did not accurately predict the thermal boundary layer upstream of the SWBLI. The effect of turbulent Prandtl number and wall temperature were studied in an attempt to improve this prediction and understand their effects on the interaction. The data showed that both parameters can significantly affect the separation size and location, but did not improve the agreement with the experiment. This case proved challenging to compute and should provide a good test for future turbulence modeling work.

Turbulent Boundary Layer↗

Wilson Corners SWMU 001 2015 Annual Long Term Monitoring Report Kennedy Space Center, Florida

This document presents the findings of the 2015 Long Term Monitoring (LTM) that was completed at the Wilson Corners site, located at the National Aeronautics and Space Administration John F. Kennedy Space Center, Florida. The objectives of the 2015 LTM event were to evaluate the groundwater flow direction and gradient, to monitor the vertical and horizontal extent of the volatile organic compounds (VOCs; including the upgradient and sidegradient extents, which are monitored every five years), and to monitor select locations internal to the dissolved groundwater plume. The 2015 LTM event included several upgradient and sidegradient monitoring wells that are not sampled annually to verify the extent of VOCs in this portion of the site. The December 2015 LTM groundwater sampling event included, depth to groundwater measurements, 40 VOC samples collected using passive diffusion bags, and one VOC sample collected using low-flow techniques. Additionally, monitoring well MW0052DD was overdrilled and abandoned using rotasonic drilling techniques. The following conclusions can be made based on the 2015 LTM results: groundwater flow is generally to the west with northwest and southwest flow components from the water table to approximately 55 feet below land surface (ft BLS); peripheral monitoring wells generally delineate VOCs to groundwater cleanup target levels (GCTLs) except for monitoring wells MW0088, MW0090, MW0095, and NPSHMW0039, which had vinyl chloride (VC) concentrations near the GCTL and MW0062, which had trichloroethene (TCE), cis-1,2-dichloroethenen (cDCE), and VC concentrations above natural attenuation default concentrations (NADCs); VOCs in interior downgradient wells generally fluctuate within historic ranges except for monitoring wells in the north-northwest portion of the site, which have increasing VC concentrations indicating potential plume migration and expansion; Historically, the vertical extents of the VOCs were delineated by monitoring wells screened greater than 60 ft BLS (MW0083 through MW0086, and MW0078). The 2015 LTM results indicate that concentrations of daughter product cDCE is greater than the NADC in MW0078 and that cDCE and VC are greater than NADCs in MW0130. TCE was greater than the GCTL in monitoring well MW130 and not detected above method detection limits (9 micrograms per Liter) in monitoring well MW0078. No GCTL exceedances were identified in monitoring wells MW0083 or MW0086; the dissolved plume footprint appears generally stable, though not fully delineated by monitoring well data in the northeast portion of the site; and 2015 LTM results generally support the existing Conceptual Site Model. Geosyntec recommends modifying the LTM program, collecting a verification sample from monitoring well MW0062, and performing a direct push technology instigation in the northnortheastern portion of the site. A cluster of monitoring wells (MW0132 [2 to 12 ft BLS], MW0133 [15 to 25 ft BLS], and MW0134 [29 to 34 ft BLS]) is proposed to delineate impacts in the northnortheast portion of the site. Geosyntec recommends installation of a vertical extent well in the center of the site (Hot Spot 2 area) post-remediation implementation.

groundwater↗

Soil Mixing with Steam and Zero Valent Iron Remediation Performance Monitoring Results at Wilson Corner, Kennedy Space Center, Florida

The National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Remediation Program implemented a groundwater interim measure between September 2014 and February 2015, to remediate a trichloroethene (TCE) groundwater source area at the Wilson Corners site. The groundwater plume is associated with the release of chlorinated solvents (specifically TCE) from historic precision cleaning and laboratory operations. A summary of the groundwater interim measure using soil mixing with steam and zero valent iron (also referred to as large diameter auger [LDA]) was presented at the 2015 Florida Remediation Conference. The objective of this presentation is to provide performance monitoring results.

Chrest, Anne M.↗

Large-Eddy Simulation of Axisymmetric Compression Corner Flow

The Wall-Modeled Large Eddy Simulation (WMLES) approach is used to study the interaction of a shock wave with a high Reynolds number turbulent boundary layer. Since the near wall region is modeled, high Reynolds number turbulent flows can be simulated at a moderate computational cost. The case considered is that of an axisymmetric Mach 2.85 turbulent boundary layer over a 30 compression corner. The Reynolds number of the boundary layer upstream of the interaction based on momentum thickness (Re theta = u sub infinity theta/v sub infinity) is ~12,000. The geometry and flow conditions match the experiments of Dunagan et al. (NASA TM 88227, 1986). The simulations were performed using equilibrium and non-equilibrium wall models. The agreement with experiment is encouraging for the finest grid with respect to the separation bubble length, unsteady shock structure and wall pressure distribution. Sensitivity ofWMLES results to grid, wall model, and blockage effects in the tunnel are reported.

Iyer, Prahladh S.↗

A Dichroic Plate with Rounded Corners for NASA’s 34m Beam Waveguide Antenna

A S/K-band frequency selective surface (FSS) or a dichroic plate is designed, manufactured and tested for use in NASA’s Deep Space Network (DSN) 34m beam waveguide (BWG) antennas. Due to its large size, the proposed dichroic incorporates a new design feature, waveguides with rounded corners to cut cost and allow ease of manufacturing the plate. The dichroic is designed using an analysis that combines the Finite Element Method (FEM) for arbitrarily shaped guides with the Method of Moments and Floquet mode theory for periodic structures. The software was verified by comparison with previously measured and computed dichroic plates. The large plate was manufactured with end-mill machining. Their RF performance was measured and is in excellent agreement with the analytical results. The dichroic has been successfully installed and in operational at three NASA Deep Space Stations.

Imbriale, William↗

Use of three-cornered hat error estimates in MERRA-2 to guide an improved reanalysis-Part 1

The three-cornered hat (3CH) method estimates the uncertainties of three different co-located model or observational data sets (Anthes and Rieckh, 2018; Sjoberg et al., 2021). Rieckh et al. (2021) used the 3CH method to compare the random error statistics of different global forecast and reanalysis models, as well as radio occultation (RO) and radiosonde observations. That study showed that the MERRA-2 reanalysis, while having smaller errors in the stratosphere than its predecessor MERRA, had larger errors in the troposphere than many of the other data sets analyzed. The MERRA-2 errors were particularly large in the tropics. In a collaborative effort between UCAR’s COSMIC (Constellation Observing System for Meteorology, Ionosphere and Meteorology) program and NASA’s Global Modeling and Assimilation Office (GMAO), we carried out further 3CH error diagnostics to help isolate the causes of these larger errors and help guide the development of an improved reanalysis. This presentation summarizes random error statistics associated with MERRA-2, ECMWF’s ERA5 reanalysis, and COSMIC-2 (C2) RO observations. We compute 3CH error variance estimates of refractivity, as well as temperature and specific humidity using UCAR’s COSMIC Data Analysis and Archive Center (CDAAC) improved 1D-variational (1D-Var) retrieval (wetPf2) over 15 latitude bands from 45S to 45N. The 1D-Var retrievals of specific humidity and temperature for C2 use NCEP’s Global Forecast System (GFS) as the background. Anthes et al. (2021) showed that it gives accurate estimates of temperature and specific humidity in the tropics and subtropics, even in the challenging environment of intense Hurricane Dorian (2019). This presentation confirms the previous results that MERRA-2 has significantly larger errors in the tropics and subtropics than either C2 or ERA5. Its errors are larger between 30S and 30N compared to 30-45 N-S latitudes, and are also larger over land compared to oceans. Most of the MERRA-2 refractivity errors come from specific humidity, except over land below 3 km where temperature errors are large. These results suggest that moist convection and atmospheric boundary layer physics in MERRA-2 may be responsible for a significant part of the higher uncertainties. These results are being used to guide GMAO in developing an improved next-generation reanalysis, as shown in a companion presentation submitted to this conference (El Akkraoui et al., 2021), which extends this study and describes improvements to MERRA-2 leading to the next GMAO reanalysis.

Jeremiah Sjoberg↗

Wilson Corners SWMU 001 2019-2020 Annual Long-Term Monitoring Report Kennedy Space Center, Florida

This report presents a summary of the long-term monitoring (LTM) activities that occurred in 2019 and 2020 at Wilson Corners, Solid Waste Management Unit 001, at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program. Adaptive site management is being utilized through ongoing assessment, design, and interim measures. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code. The goal of LTM at this site is threefold: to determine groundwater flow characteristics, monitor the downgradient concentration trends, and monitor select locations internal to the groundwater plume. Every 5 years, upgradient and side-gradient monitoring wells are sampled to verify delineation. The last time this was performed was in 2015. Sampling of these wells in 2020 was replaced with the direct push technology investigations in October 2020 and April 2021. The activities presented in this report include three field events: (1) December 2019 -groundwater gauging of 38 monitoring wells and sampling of 36 monitoring wells; (2) May 2020 - groundwater sampling of 7 monitoring wells; and (3) December 2020 - groundwater gauging of 49 monitoring wells and sampling of 43 monitoring wells. During the December 2019 and May 2020 events, monitoring wells were sampled using passive diffusion bags and were analyzed for a “full list” of volatile organic compounds (VOCs), including Freon 113. During the December 2020 event, the low flow sampling method was used, and samples were analyzed for a “select list” of VOCs, including Freon 113. The following conclusions can be made based on the 2019 and 2020 LTM results: •In December 2019 and December 2020, groundwater flow for the site was generally to the west with the individual zones only varying by occasional northerly and southerly components. This is generally consistent with historical observations at the site. •The GCTL plume continues to extend both horizontally and vertically beyond our current monitoring well network. •The vertical extent of VOCs was historically generally delineated by monitoring wells screened greater than 48 feet bls. The results from the two vertical extent monitoring wells WILC-MW0078 and WILC-MW0130 that were sampled during the 2019 and 2020 LTM indicate that groundwater VOC concentrations in both wells were greater than the GCTL. •Freon 113 was not detected above GCTLs during the 2019 and 2020 LTM events. Based on groundwater sampling activities performed during this reporting period, including recent DPT groundwater sampling conducted for the implementation of an air sparge system, the following recommendations are provided: •Install 10 new monitoring wells, which will be sampled along with 49 existing monitoring wells, to assist with delineation of the low concentration plume. The wells are listed inTable 4-1, and the proposed locations are presented on Figures4 -1 through 4-5. (Figures 4-1, 4-2, 4-3, and 4-5 also show updated plumes and proposed performance monitoring well locations. This information will be discussed and presented under a separate cover.) •Modify the annual LTM sampling plan as presented inTable 4-1. •Sampling for future events at the site will be conducted using low flow pumping methods. The next annual LTM sampling event is currently planned for December 2021. Please note the 10 new monitoring wells will not be installed before this event but will be installed as part of the upcoming IM construction and will be sampled during baseline sampling, along with the 49 existing monitoring wells. Following this sampling event, it is recommended that the Annual LTM be combined with the performance monitoring under the IM implementation, and LTM be temporarily discontinued. Objectives of the 2021 LTM are to: (i) evaluate groundwater gradient and flow direction by collecting depth to water measurements from LTM wells; (ii) continue monitoring the peripheral VOC trends in the northern, southern, and western portions of the site by monitoring existing wells and installing and monitoring new wells as recommended; and (iii) monitor select internal plume wells.

Jennifer Lynn Joyal↗

Wilson Corners Solid Waste Management Unit (SWMU) 001: 2021 Annual Long-Term Monitoring Report, Kennedy Space Center, Florida

This report presents a summary of the long-term monitoring (LTM) activities that occurred in 2021 at Wilson Corners, Solid Waste Management Unit (SWMU) 001, at Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program. Adaptive site management is being utilized through ongoing assessment, design, and interim measures (IM). Annual LTM of the groundwater is also being conducted at the site. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code (F.A.C.). The goal of LTM at this site is threefold: to determine groundwater flow characteristics, monitor the downgradient concentration trends, and monitor select locations internal to the groundwater plume. Every 5 years, upgradient and side-gradient monitoring wells are sampled to verify delineation. The last time this was performed was in 2015. The sampling of these wells in 2020 was replaced with the direct push technology (DPT) investigations completed in October 2020 and April 2021. This DPT groundwater data was presented in an Advance Data Package (ADP) in September 2021 and discussed in the Implementation Work Plan (IWP) dated November 2021 for installation of an air sparge (AS) system. Based on results from groundwater sampling activities performed during the previous reporting period, including the 2020 and 2021 DPT groundwater sampling, it was determined that the LTM sampling plan was no longer meeting the goal of LTM because delineation was not verified. The 2021 LTM sampling plan was modified to include the sampling of monitoring wells located around the perimeter of the low concentration plume (LCP); the area with concentrations of contaminants of concern [COCs] greater than Groundwater Cleanup Target Levels [GCTLs]), and sampling of 10 monitoring wells proposed for installation (April 2021 KSC Remediation Team (KSCRT) Meeting, Decision 2104-D32). The modified LTM plan received team consensus at the September 2021 KSCRT Meeting (Decision Number 2109-D03), and sampling of the existing monitoring wells was completed in December 2021. The proposed monitoring wells are planned for installation in late 2022, concurrent with ongoing IM construction activities. December 2021 LTM data was presented at the May 2022 KSCRT Meeting, and activities are summarized in this report. The activities presented in this report include the December 2021 groundwater gauging of 42 monitoring wells and sampling of 44 monitoring wells. During the December 2021 event, the low flow sampling method was used, and samples were analyzed for a select list of volatile organic compounds (VOCs), including 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113). The following conclusions can be made based on the 2021 LTM results: - In December 2021, groundwater flow for the site was generally to the west at all intervals. This is generally consistent with historical observations at the site, with the exception of a southwest and southeast flow component observed at 34 to 48 feet below land surface (bls). - The vertical extent of VOCs was historically delineated by monitoring wells screened greater than 48 feet bls. The results from the two vertical extent monitoring wells, WILC-MW0078 (screened 65 to 70 feet bls) and WILC-MW0130 (screened 56 to 66 feet bls) that were sampled during the 2021 LTM indicate that groundwater vinyl chloride (VC) concentrations in both wells were greater than the GCTL. The Remediation Team has previously agreed to delay deeper DPT investigations in this area to prevent the creation of additional pathways for vertical migration. - The LCP continues to extend both horizontally, predominantly to the west, and vertically beyond the current monitoring well network, with some retraction observed to the southeast. Evaluation of this data combined with data from the 2020 and 2021 DPT sampling event indicate that the LCP encompasses an estimated 20.7 acres based on an expanded sampling area, as compared to the 2020 LCP footprint of 17.0 acres. - Freon 113 was not detected above GCTLs during the 2021 LTM event. Based on groundwater sampling activities performed in 2021, including April 2021 DPT groundwater sampling, the following recommendations are provided: - Perform the next LTM sampling event, targeted to occur in 2023, concurrently with the IM baseline sampling prior to AS system installation; - Include sampling from nine monitoring wells that are planned to be installed in late 2022, concurrent with upcoming IM construction activities. Installation of one deep vertical well, screened 70 to 80 feet bls, will be delayed to prevent the creation of an additional pathway for vertical migration; - Continue to sample under the modified annual LTM plan as presented in Table 4-1 concurrently with IM baseline sampling; and - Once the AS system install and start-up is complete, select monitoring wells from the LTM program will transition into the performance monitoring plan, and LTM will be temporarily discontinued. Performance monitoring will be performed quarterly, and the monitoring well network will be evaluated following the first performance monitoring sampling event.

long-term monitoring (LTM)↗

Wilson Corners, Solid Waste Management Unit 001(SWMU 01) 2023 Annual Long-Term Monitoring Report

This report presents a summary of the long-term monitoring (LTM) activities that occurred in 2023 at Wilson Corners, Solid Waste Management Unit 001, at Kennedy Space Center (KSC), Florida. Annual LTM of groundwater is being conducted at the site. Based on results from groundwater sampling activities performed during the 2019 through 2020 LTM reporting period and the 2020 and 2021 DPT groundwater sampling, it was determined that the LTM sampling plan was no longer meeting the goal of LTM because delineation was not verified and the installation of an air sparge (AS) system to treat the area of the High Concentration Plume was recommended. The AS System was installed in late 2022 and early 2023. System start-up activities were initiated in April 2023. Following system startup, several site wells required retrofitting to equip wellheads for withstanding the air pressure released from air sparge wells during system operation. Some site wells also required repair or abandonment, and replacement. Survey of location and top-of-casing of newly installed monitoring wells was combined with scheduled AS system survey activities and was completed in January 2024. The activities presented in this report include the February and April 2023 LTM monitoring well installations; March and April 2023 LTM and performance monitoring well water level gauging and sampling; November 2023 LTM well retrofits and repairs; a summary of December 2023 LTM well abandonments and installations (complete site well abandonment activities will be presented under a separate cover); and January 2024 LTM well survey. During the March and April 2023 sampling events, the low-flow sampling method was used, and samples were analyzed for a select list of volatile organic compounds. In March 2023, groundwater flow for the site was generally to the west was generally consistent with historical observations at the site. The Low Concentration Plume (LCP) continues to extend both horizontally and vertically beyond the terminal depth of the current monitoring well network. Data, inclusive of the 2023 LTM and baseline performance monitoring sampling events, indicate that the LCP encompasses an estimated 19.5 acres, compared to the 2021 LCP footprint, inclusive of the 2020 and 2021 DPT sampling events of 20.7 acres. The vertical extent of VOCs was historically delineated by monitoring wells screened greater than 48 feet below land surface (bls). The results from the three vertical extent monitoring wells screened below 48 feet bls that were sampled during the 2023 LTM indicate that groundwater vinyl chloride concentrations in these three wells are greater than the GCTL. As presented in the 2021 Long-Term Monitoring Report (NASA 2022), the KSCRT agreed to delay deeper investigations in this area to prevent the creation of additional pathways for vertical migration. Based on groundwater sampling activities performed in 2023, recommendations are to perform the next annual LTM sampling event, scheduled for April 2024 and to conduct quarterly performance monitoring of the AS System. The current selection of monitoring wells in the recommended 2024 LTM plan will provide an adequate data set for monitoring groundwater plume behavior; however, the LTM monitoring well network will be evaluated and refined based on 2024 LTM and year one performance monitoring data.

King Linnea↗

Cornering (quasi) degenerate neutrinos with cosmology

In light of the improved sensitivities of cosmological observations, we examine the status of quasi-degenerate neutrino mass scenarios. Within the simplest extension of the standard cosmological model with massive neutrinos, we find that quasi-degenerate neutrinos are severely constrained by present cosmological data and neutrino oscillation experiments. We find that Planck 2018 observations of cosmic microwave background (CMB) anisotropies disfavour quasi-degenerate neutrino masses at 2.4 Gaussian >σ’s, while adding baryon acoustic oscillations (BAO) data brings the rejection to 5.9 σ’s. The highest statistical significance with which one would be able to rule out quasi-degeneracy would arise if the sum of neutrino masses is Σm v = 60 meV (the minimum allowed by neutrino oscillation experiments); indeed a sensitivity of 15 meV, as expected from a combination of future cosmological probes, would further improve the rejection level up to 17σ. We discuss the robustness of these projections with respect to assumptions on the underlying cosmological model, and also compare them with bounds from β decay endpoint and neutrinoless double beta decay studies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The Ce-Fe-Ti System: Phase Equilibria in the Fe-rich Corner at 1000 °C

The rare earth–iron–transition metal systems are of increasing interest in the search for novel permanent magnet phases. This work reports on the solidification behavior, phase equilibria and stability range of solid phases in the ternary Ce-Fe-Ti system, focusing on the iron-rich region (> 65 at.% Fe) of the isothermal section at 1000 °C. Further, two ternary phases Ce 1.03 Fe 12-x Ti x (x = 0.87–1.02) with ThMn 12 structure type and Ce 3.06 Fe 27.6 Ti 1.4 with Nd 3 Fe 29 structure type were observed. Magnetic measurements of Ce 1.03 Fe 12-x Ti x and Ce 3.06 Fe 27.6 Ti 1.4 revealed ferromagnetic ordering with Curie temperatures of 550 K and 327 K, respectively.

36 MATERIALS SCIENCE↗

First-principles analysis of the Al-rich corner of Al-Li-Cu phase diagram

The phase diagram of Al-Li-Cu system in the Al-rich region was determined by means of first-principles calculations and statistical mechanics. The mixing enthalpies of many configurations for different lattices in the whole Al-Li-Cu system were determined by density functional theory simulations to find the stable phases in the convex hull. They were fitted with a cluster expansion to calculate the free energy of the configurations with different compositions as a function of temperature in the Al-rich region (Al content > 40 at.%) by means of Monte Carlo simulations. It was found that the ground state phases in the Al-rich part of the Al-Li-Cu phase diagram were α-Al, θ' (Al 2 Cu), $δ$' (Al 3 Li), $δ$ (AlLi) and T 1 (Al 6 Cu 4 Li 3 ), while θ'' (Al 3 Cu), T 1' (Al 2 CuLi) and Al 3 Cu 2 Li were found on the lowest mixing enthalpy surfaces of their lattices and were metastable. α-Al, $δ$ and T 1 are stable phases in the whole temperature range while $δ$' becomes metastable at very low temperature and θ (Al 2 Cu) replaces θ' as the stable phase at approximately 550 K due to the vibrational entropic contribution. In addition, the phase diagram in the Al-rich region was built and it was shown in isothermal sections from 100 to 900 K. They were in good agreement with the limited experimental data in the literature and provided new information regarding the stability, solubility and stoichiometry of the different phases. This information is important to understand the precipitation mechanisms during high temperature aging.

36 MATERIALS SCIENCE↗

Not Cutting Corners: Bioderived Triggers Driving Oxidative Main Chain Scission of Poly(ethylene terephthalate)

About 20–34 billion poly(ethylene terephthalate) (PET) bottles from the beverage industry leak into aquatic ecosystems annually, necessitating the development of urgent strategies to treat waterborne plastic pollution. Inspired by the scalability of water disinfection infrastructure and protocols, we present a dual depolymerization approach relying on oxidation, followed by hydrolysis. Incorporating bioderived monounsaturated C18 diacid (C18:1-DA) counits at low dosages (2–5%) in the PET backbone overcomes the diffusional limitations of depolymerizing PET in the solid state by suppressing the glass transition temperature of the copolymer by 20 °C. Cryomilled C18:1-PET powder suspended in an oxidant-loaded alkaline slurry underwent bulk depolymerization to oligomers at 80–100 °C via oxidative scissions at the internally located unsaturations. In contrast, conventional PET undergoes only minor end-chain scission under mild alkaline conditions. These oligomers are suitable for low-energy repolymerization or facile solvolysis to monomers. A permanganate-periodate oxidant couple demonstrated successful oxidation through the bulk of the polymer, which subsequently was hydrolyzed to monomers. Furthermore, this model system serves as a proxy for ozonolysis, followed by mild hydrolysis to reduce the energetics of alkaline hydrolysis. This integrated oxidation–hydrolysis strategy paves the way for the industrial adoption of cleaner, advanced oxidation processes, such as ozonolysis for plastic pretreatment, further enabling commercialized chemical recycling of unsaturation-containing polyesters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗