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DOE OSTI2017

Degradation Analysis of Field-Exposed Photovoltaic Modules with Non-Fluoropolymer-Based Backsheets

The selection of polymeric materials utilized in photovoltaic (PV) modules has changed relatively little since the inception of the PV industry, with ethylene-vinyl acetate (EVA), polyethylene terephthalate (PET), and fluoropolymer-based laminates being the most widely adopted primary components of the encapsulant and backsheet materials. The backsheet must serve to electrically insulate the solar cells and protect them from the effects of weathering. Due to continued downward pressure on cost, other polymeric materials are being formulated to withstand outdoor exposure for use in backsheets to replace either the PET film, the fluoropoymer film, or both. Because of their relatively recent deployment, less is known about their reliability and if they are durable enough to fulfill the greater than or equal to 25 year warranties of current PV modules. This work presents a degradation analysis of field-exposed modules with polyamide- and polyester-based backsheets. Modules were exposed for up to five years in different geographic locations: USA (Maryland, Ohio), China, and Italy. Surface and cross-sectional analysis included visual inspection, colorimetry, glossimetry, and Fourier-transform infrared spectroscopy. Each module experienced different types of degradation depending on the exposure site, even for the same material and module brand. For instance, the polyamide-based backsheet experienced hairline cracking and greater yellowing and chemical changes in China (Changsu, humid subtropical climate), while in Italy (Rome, hot-summer Mediterranean climate) it underwent macroscopic cracking and greater losses in gloss. Spectroscopic studies have permitted identification of degradation products and changes in polymer structure over time. Comparisons are made to fielded modules with fluoropolymer-based backsheets, as well as backsheet materials in accelerated laboratory exposures. Implications for qualification testing and service life prediction of the non-fluoropolymer-based backsheets are discussed.

14 SOLAR ENERGY↗

DOE OSTI2015

Angular dependence of dose sensitivity of nanoDot optically stimulated luminescent dosimeters in different radiation geometries

Purpose: A type of in vivo dosimeter, an optically stimulated luminescent dosimeter, OSLD, may have dose sensitivity that depends on the angle of incidence of radiation. This work measures how angular dependence of a nanoDot changes with the geometry of the phantom in which irradiation occurs and with the intrinsic structure of the nanoDot. Methods: The OSLDs used in this work were nanoDot dosimeters (Landauer, Inc., Glenwood, IL), which were read with a MicroStar reader (Landauer, Inc., Glenwood, IL). Dose to the OSLDs was delivered by 6 MV x-rays. NanoDots with various intrinsic sensitivities were irradiated in numerous phantoms that had geometric shapes of cylinders, rectangles, and a cube. Results: No angular dependence was seen in cylindrical phantoms, cubic phantoms, or rectangular phantoms with a thickness to width ratio of 0.3 or 1.5. An angular dependence of 1% was observed in rectangular phantoms with a thickness to width of 0.433–0.633. A group of nanoDots had sensitive layers with mass density of 2.42–2.58 g/cm{sup 3} and relative sensitivity of 0.92–1.09 and no difference in their angular dependence. Within experimental uncertainty, nanoDot measurements agree with a parallel-plate ion chamber at a depth of maximum dose. Conclusions: When irradiated in cylindrical, rectangular, and cubic phantoms, nanoDots show a maximum angular dependence of 1% or less at an incidence angle of 90°. For a sample of 78 new nanoDots, the range of their relative intrinsic sensitivity is 0.92–1.09. For a sample of ten nanoDots, on average, the mass in the sensitive layer is 73.1% Al{sub 2}O{sub 3}:C and 26.9% polyester. The mass density of the sensitive layer of a nanoDot disc is between 2.42 and 2.58 g/cm{sup 3}. The angular dependence is not related to Al{sub 2}O{sub 3}:C loading of the nanoDot disc. The nanoDot at the depth of maximum dose has no more angular dependence than a parallel-plate ion chamber.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2016

Endoluminal ultrasound applicators for MR-guided thermal ablation of pancreatic tumors: Preliminary design and evaluation in a porcine pancreas model

Purpose: Endoluminal ultrasound may serve as a minimally invasive option for delivering thermal ablation to pancreatic tumors adjacent to the stomach or duodenum. The objective of this study was to explore the basic feasibility of this treatment strategy through the design, characterization, and evaluation of proof-of-concept endoluminal ultrasound applicators capable of placement in the gastrointestinal (GI) lumen for volumetric pancreas ablation under MR guidance. Methods: Two variants of the endoluminal applicator, each containing a distinct array of two independently powered transducers (10 × 10 mm 3.2 MHz planar; or 8 × 10 × 20 mm radius of curvature 3.3 MHz curvilinear geometries) at the distal end of a meter long flexible catheter assembly, were designed and fabricated. Transducers and circulatory water flow for acoustic coupling and luminal cooling were contained by a low-profile polyester balloon covering the transducer assembly fixture. Each applicator incorporated miniature spiral MR coils and mechanical features (guiding tips and hinges) to facilitate tracking and insertion through the GI tract under MRI guidance. Acoustic characterization of each device was performed using radiation force balance and hydrophone measurements. Device delivery into the upper GI tract, adjacent to the pancreas, and heating characteristics for treatment of pancreatic tissue were evaluated in MR-guided ex vivo and in vivo porcine experiments. MR guidance was utilized for anatomical target identification, tracking/positioning of the applicator, and MR temperature imaging (MRTI) for PRF-based multislice thermometry, implemented in the real-time RTHawk software environment. Results: Force balance and hydrophone measurements indicated efficiencies of 48.8% and 47.8% and −3 dB intensity beam-widths of 3.2 and 1.2 mm for the planar and curvilinear transducers, respectively. Ex vivo studies on whole-porcine carcasses revealed capabilities of producing ablative temperature rise (ΔT > 15 °C) contours in pancreatic tissue 4–40 mm long and 4–28 mm wide for the planar transducer applicator (1–13 min sonication duration, ∼4 W/cm{sup 2} applied acoustic intensity). Curvilinear transducers produced more selective heating, with a narrower ΔT > 15 °C contour length and width of up to 1–24 mm and 2–7 mm, respectively (1–7 min sonication duration, ∼4 W/cm{sup 2} applied acoustic intensity). Active tracking of the miniature spiral coils was achieved using a Hadamard encoding tracking sequence, enabling real-time determination of each coil’s coordinates and automated prescription of imaging planes for thermometry. In vivo MRTI-guided heating trials in three pigs demonstrated capability of ∼20 °C temperature elevation in pancreatic tissue at 2 cm depths from the applicator, with 5–7 W/cm{sup 2} applied intensity and 6–16 min sonication duration. Dimensions of thermal lesions in the pancreas ranged from 12 to 28 mm, 3 to 10 mm, and 5 to 10 mm in length, width, and depth, respectively, as verified through histological analysis of tissue sections. Multiple-baseline reconstruction and respiratory-gated acquisition were demonstrated to be effective strategies in suppressing motion artifacts for clear evolution of temperature profiles during MRTI in the in vivo studies. Conclusions: This study demonstrates the technical feasibility of generating volumetric ablation in pancreatic tissue using endoluminal ultrasound applicators positioned in the stomach lumen. MR guidance facilitates target identification, device tracking/positioning, and treatment monitoring through real-time multislice PRF-based thermometry.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2024

Chemical recycling of mixed textile waste

Globally, less than 0.5% of postconsumer textile waste is recycled, with the majority incinerated or ending up in landfills. Most postconsumer textiles are mixed fibers, complicating mechanical recycling due to material blends and contaminants. Here, we demonstrate the chemical conversion of postconsumer mixed textile waste using microwave-assisted glycolysis over a ZnO catalyst followed by solvent dissolution. This approach electrifies the process heat while allowing rapid depolymerization of polyester and spandex to their monomers in 15 minutes. A simple solvent dissolution enables the separation of cotton and nylon. We assess the quality of all components through extensive material characterization, discuss their potential for sustainable recycling, and provide a techno-economic analysis of the economic feasibility of the process.

Science & Technology - Other Topics↗

DOE OSTI2024

Manufacture and testing of biomass-derivable thermosets for wind blade recycling

Wind energy is helping to decarbonize the electrical grid, but wind blades are not recyclable, and current end-of-life management strategies are not sustainable. Here, to address the material recyclability challenges in sustainable energy infrastructure, we introduce scalable biomass-derivable polyester covalent adaptable networks and corresponding fiber-reinforced composites for recyclable wind blade fabrication. Through experimental and computational studies, including vacuum-assisted resin-transfer molding of a 9-meter wind blade prototype, we demonstrate drop-in technological readiness of this material with existing manufacture techniques, superior properties relative to incumbent materials, and practical end-of-life chemical recyclability. Most notable is the counterintuitive creep suppression, outperforming industry state-of-the-art thermosets despite the dynamic cross-link topology. Overall, this report details the many facets of wind blade manufacture, encompassing chemistry, engineering, safety, mechanical analyses, weathering, and chemical recyclability, enabling a realistic path toward biomass-derivable, recyclable wind blades.

17 WIND ENERGY↗

DOE OSTI2020

m2p (Monomers to Polymers)

The software is Python-based code that takes monomers, represented as SMILES, and "reacts" them together to form long polymer chains, represented as SMILES, based on known polymer chemistries. The software is used in a machine-learning pipeline where a database and machine-learning approaches are used to predict polymer properties base on molecular structure. This software is necessary to represent the polymer chain, instead of simple repeat units, as the software statistically represents different molecular architectures that occur during reactions (e.g. head-to-head, head-to-tail, and tail-to-tail). It is capable of building polymer chains with five different chemistries: vinyl/olefin, polyamide, polycarbonate, polyester, and polyimides. The user is able to specify different monomer pairings and degree of polymerization for different polymer chains.

Wilson, Nolan↗

DOE OSTI2024

Moving toward automated µFTIR spectra matching for microplastic identification: addressing false identifications and improving accuracy

Abstract Infrared spectroscopy is a widely used tool for studying microplastics and identifying microparticles. Researchers rely on spectral libraries to differentiate between synthetic and natural materials. Unfortunately, spectral library matching is not perfect, and best practices require researchers to use time consuming, manual peak matching to assess spectral matches. Moving toward automated matching requires increased confidence in the matching process. Using spectra matching software may increase the efficiency of particle identification, however some matching strategies may confuse natural materials such as cotton, silk, and plant matter with common classes of synthetics such as polyesters and polyamides. In this experiment, we prepared 22 pristine sample materials from natural and synthetic sources and measured micro-Fourier transform infrared (µFTIR) spectra in transmission mode for each sample using a Thermo Nicolet iN10 MX instrument. The collected spectra were then input into two spectral library matching systems (Omnic Picta and Open Specy), using a total of five identification routines. Next, we placed a subset of four pristine microplastic materials in a biologically active river system for two weeks to simulate environmental samples. These simulated environmental samples were processed using 10% hydrogen peroxide for 24 h to remove organic contamination and then identified using the strongest performing library. We found that libraries with fewer sample spectra produced lower correlation matches and that using derivative correction greatly reduced the number of inaccuracies in identifying materials as either natural or synthetic. We also found that environmental fouling reduced the correlation value of library matches when compared to pristine particles, however the effect was not consistent across the four materials tested. Overall, we found that the accuracy of automated library matching in the tested systems and processing routines varied from 64.1 to 98.0% for distinguishing between natural and synthetic materials, and that a high Hit Quality Index (HQI) did not always correlate with accuracy. These results are important for the microplastic field, demonstrating a need to rigorously test spectral libraries and processing routines with known materials to ensure identification accuracy.

Kozloski, Rachel↗

DOE OSTI2025

Engineering the green algae Chlamydomonas incerta for recombinant protein production

Chlamydomonas incerta , a genetically close relative of the model green alga Chlamydomonas reinhardtii , shows significant potential as a host for recombinant protein expression. Because of the close genetic relationship between C. incerta and C. reinhardtii , this species offers an additional reference point for advancing our understanding of photosynthetic organisms, and also provides a potential new candidate for biotechnological applications. This study investigates C. incerta ’s capacity to express three recombinant proteins: the fluorescent protein mCherry, the hemicellulose-degrading enzyme xylanase, and the plastic-degrading enzyme PHL7. We have also examined the capacity to target protein expression to various cellular compartments in this alga, including the cytosol, secretory pathway, cytoplasmic membrane, and cell wall. When compared directly with C. reinhardtii , C. incerta exhibited a distinct but notable capacity for recombinant protein production. Cellular transformation with a vector encoding mCherry revealed that C. incerta produced approximately 3.5 times higher fluorescence levels and a 3.7-fold increase in immunoblot intensity compared to C. reinhardtii . For xylanase expression and secretion, both C. incerta and C. reinhardtii showed similar secretion capacities and enzymatic activities, with comparable xylan degradation rates, highlighting the industrial applicability of xylanase expression in microalgae. Finally, C. incerta showed comparable PHL7 activity levels to C. reinhardtii , as demonstrated by the in vitro degradation of a polyester polyurethane suspension, Impranil® DLN. Finally, we also explored the potential of cellular fusion for the generation of genetic hybrids between C. incerta and C. reinhardtii as a means to enhance phenotypic diversity and augment genetic variation. We were able to generate genetic fusion that could exchange both the recombinant protein genes, as well as associated selectable marker genes into recombinant offspring. These findings emphasize C. incerta ’s potential as a robust platform for recombinant protein production, and as a powerful tool for gaining a better understanding of microalgal biology.

cell membranes↗

DOE OSTI2013

Enhancements in Glovebox Design Resulting from Laboratory-Conducted FIre Tests

The primary mission of the Pit Disassembly and Conversion Facility (PDCF) Project was to disassemble nuclear weapons pits and convert the resulting special nuclear materials to a form suitable for further disposition. Because of the nature of materials involved, the fundamental system which allowed PDCF to perform its mission was a series of integrated and interconnected gloveboxes which provided confinement and containment of the radioactive materials being processed. The high throughput planned for PDCF and the relatively high neutron and gamma radiation levels of the pits required that gloveboxes be shielded to meet worker dose limits. The glovebox shielding material was required to contain high hydrogen concentrations which typically result in these materials being combustible. High combustible loadings created design challenges for the facility fire suppression and ventilation system design. Combustible loading estimates for the PDCF Plutonium (Pu) Processing Building increased significantly due to these shielding requirements. As a result, the estimates of combustible loading substantially exceeded values used to support fire and facility safety analyses. To ensure a valid basis for combustible loading contributed by the glovebox system, the PDCF Project funded a series of fire tests conducted by the Southwest Research Institute on door panels and a representative glovebox containing Water Extended Polyester (WEP) radiological shielding to observe their behavior during a fire event. Improvements to PDCF glovebox designs were implemented based on lessons learned during the fire test. In particular, methods were developed to provide high levels of neutron shielding while maintaining combustible loading in the glovebox shells at low levels. Additionally, the fire test results led to design modifications to mitigate pressure increases observed during the fire test in order to maintain the integrity of the WEP cladding. These changes resulted in significantly reducing the credited combustible loading of the facility. These advances in glovebox design should be considered for application in nuclear facilities within the Department of Energy complex in the future.

Brooks, Kriston P.↗

DOE OSTI2014

Advancing Renewable Materials by Light and X-ray Scattering

With the ultimate goal to design PHA polymer nanocomposites with tailored properties, we have completed systematic study of the influence of cooling rate [Xie et al, J. Appl. Poly. Sci., 2008] and nanofiller [Xie et al, Polymer 2009] characteristics on model bionanocomposites. Structure-property relationships for a model bionanocomposites system were investigated. These results yielded new fundamental knowledge that supports the discovery of cost-effective manufacturing technologies for a family of promising polyhydroxyalkanoates (PHAs) polyesters, with the potential to replace polyethylene and polypropylene (see Noda letter). Our results show that simple two-phase composite models do not account for the data. Although improvement of the mechanical properties (stiffness/modulus and toughness) must be due to alteration of the matrix by the nanoparticle filler, the observed improvement was not caused by the change of crystallinity or spherulitic morphology. Instead, improvement depends on the molecular weight of the polymer matrix and unknown filler-matrix interactions.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Mechanistic studies aimed at the development of single site metal alkoxide catalysts for the production of polyoxygenates from renewable resources.

The work proposed herein follows on directly from the existing 3 year grant and the request for funding is for 12 months to allow completion of this work and graduation of current students supported by DOE. The three primary projects are as follows. 1.) A comparative study of the reactivity of LMg(OR) (solvent), where L= a β-diiminate or pyrromethene ligand, in the ring-opening of cyclic esters. 2.) The homopolymerization of expoxides, particularly propylene oxide and styrene oxide, and their copolymerizations with carbon dioxide or organic anhydrides to yield polycarbonates or polyesters, respectively. 3.) The development of well-defined bismuth (III) complexes for ring-opening polymerizations that are tolerant of both air and water. In each of these topics special emphasis is placed on developing a detailed mechanistic understanding of the ring-opening event and how this is modified by the employment of specific metal and ligand combinations. This document also provides a report on findings of the past grant period that are not yet in the public domain/published and shows how the proposed work will bring the original project to conclusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Dosimetry in Thermal Neutron Irradiation Facility at BMRR

Radiation dosimetry for Neutron Capture Therapy (NCT) has been performed since 1959 at Thermal Neutron Irradiation Facility (TNIF) of the three-megawatt light-water cooled Brookhaven Medical Research Reactor (BMRR). In the early 1990s when more effective drug carriers were developed for NCT, in which the eye melanoma and brain tumors in rats were irradiated in situ, extensive clinical trials of small animals began using a focused thermal neutron beam. To improve the dosimetry at irradiation facility, a series of innovative designs and major modifications made to enhance the beam intensity and to ease the experimental sampling at BMRR were performed; including (1) in-core fuel addition to increase source strength and balance flux of neutrons towards two ports, (2) out of core moderator remodeling, done by replacing thicker D 2 O tanks at graphite-shutter interfacial areas, to expedite neutron thermalization, (3) beam shutter upgrade to reduce strayed neutrons and gamma dose, (4) beam collimator redesign to optimize the beam flux versus dose for animal treatment, (5) beam port shielding installation around the shutter opening area (lithium-6 enriched polyester-resin in boxes, attached with polyethylene plates) to reduce prompt gamma and fast neutron doses, (6) sample holder repositioning to optimize angle versus distance for a single organ or whole body irradiation, and (7) holder wall buildup with neutron reflector materials to increase dose and dose rate from scattered thermal neutrons. During the facility upgrade, reactor dosimetry was conducted using thermoluminescent dosimeters TLD for gamma dose estimate, using ion chambers to confirm fast neutron and gamma dose rate, and by the activation of gold-foils with and without cadmium-covers, for fast and thermal neutron flux determination. Based on the combined effect from the size and depth of tumor cells and the location and geometry of dosimeters, the measured flux from cadmium-difference method was 4 - 7 % lower than the statistical mean derived from the Monte-Carlo modeling (5% uncertainty). The dose rate measured by ion chambers was 6 - 10 % lower than the output tallies (7% uncertainty). The detailed dosimetry that was performed at the TNIF for the NCT will be described.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2016

SDU6 Interior Liner Testing & Evaluation

Two liner materials (Marseal® M-3500 and REMA Chemoline® 4CN) proposed for use as a liner inside the Saltstone Disposal Unit 6 (SDU6) were subjected to specific ASTM tests (tensile and lap-shear) after immersion in 50% and 100% simulant solutions for 1000 hours at the Savannah River Ecology Laboratory. Both liner materials exhibited good resistance to the simulant chemistry, at least based on the tests performed and the test duration/conditions imposed. In lap-shear tests, both materials failed in the base material rather than peeling apart, confirming good adhesion. The REMA 4CN bromobutyl elastomer showed superior bonding characteristics and absence of warping or delamination at the conditions tested. The Marseal M-3500 material (PVC/EVA blend with polyester reinforcement) exhibited deformation and debonding in some locations. The cause of the deformation and delamination observed in the Marseal M-3500 material is not fully known, but possibly attributed to thermomechanical stress at immersion temperatures, and the thermoplastic nature of the material. The immersion temperature (68 °C) is slightly greater than the maximum use temperature limit quoted for the Marseal M- 3500 liner (65 °C), though the basis for the service limit is unknown. The testing performed was limited in scope and only for these two liner materials. These tests were primarily performed to screen for severe incompatibility or short-term degradation in Saltstone bleedwater simulants at bounding solution temperatures. Additional testing is recommended to assess long-term performance and the overall service life of the liner.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

Catalytic Upgrading of Key Biorefining Building Blocks to Renewable Chemicals, Polymeric Materials, and Liquid Fuels

The central objective of this project is to develop efficient, selective, and cost-effective catalytic systems for upgrading of key biorefining building blocks derived from catalytic conversion of plant biomass into value-added chemicals, polymeric materials, and liquid fuels. More specifically, the proposed work for the current grant period seeks to accomplish the following three specific objectives: (a) developing cost-effective and recyclable catalysts for selective upgrading (direct coupling) of the C 6 biorefining building block 5-hydroxymethylfurfural (HMF) into C 12 intermediates and for integrating biomass conversion and upgrading processes; (b) transforming the upgraded C 12 intermediates into polyols, polyurethanes, polyesters, and diesel fuels; and (c) reforming the upgraded intermediates into premium C 12 centered liquid hydrocarbon transportation fuels via selective hydrodeoxygenation catalysis.

09 BIOMASS FUELS↗

DOE OSTI2022

A Novel Process for Converting Coal to High-Value Polyurethane Products

Battelle has demonstrated a patented process for making high-value, polyurethane (PU) foam from coal, based on preparing liquefied coal via direct liquefaction, converting it to polyols as an intermediate via ozonation, and then making PU foams from these polyols. This process represents a breakthrough in innovative utilization of U.S. coals, and is applicable to bituminous as well as sub-bituminous coals. The resulting PU foam products are projected to have an extremely high value (i.e., over $\$5,000$ /ton), with nearly 100% of carbon utilization from coalderived liquid feedstock, and 31.5% to 43.5% of the carbon in the PU foam polyol product being bio-based. The targeted products represent an extremely large (i.e., over $80 billion/year), existing PU foam market, which could expand into making coatings and adhesives. The process can further help reduce petroleum imports, while improving the economics of PU foam production. This work was completed with funding from the National Energy Technology Laboratory (NETL), with cost share from the State of Ohio’s Ohio Development Services Agency (ODSA) and others, and has advanced the process to 10 kg/day continuous scale and thus to Technology Readiness Level (TRL) 5. A total of 48 coal-based polyols were prepared and evaluated. The initial 28 polyols focused on range finding for ideal conditions. The later 20 polyols were produced as part of process optimizations. These optimizations were targeted around a continuous ozonolysis process to evaluate extended time reactions and to create the necessary intermediate for production of 1-gallon samples of polyol. The most unique attribute of Battelle’s polyol is in the utilization of coal’s aromaticity to gain final foam rigidity. Typically, polyols depend on the isocyanate fraction and cross-linking to gain rigidity. By utilizing coal, we were able to maintain rigidity while reducing the overall hydroxyl value of the polyol. This is important as lower hydroxyl value leads to greater percent weight of the coal-based polyol because less isocyanate is required for foaming. This leads to greater foam cost savings. This report provides the details, process, and process cost models of the conversion of coal to polyols and further to PU foams. Battelle’s process begins with coal liquids. These liquids can be obtained by two processes: coal coking or pyrolysis to produce coal tar, and Battelle’s biobased coal-to-liquids (CTL) process to produce heavy syncrude after liquifying >85% coal. After liquification, Battelle utilizes ozonolysis to create functionalization on the polyaromatic coal structure. The functionalization is then converted to the final polyester polyol through transesterification, or to hydroxyamide polyol through amidification. Equivalent or better standard properties have been obtained for 2 lb/ft 3 density rigid, water and freon-alternative blown foams, including compressive strength, density, R-value, and dimensional stability. Target applications for these foams are insulation, packaging, and energy-absorbing foams. Some exploratory testing also showed promise for adhesives applications. A detailed economic analysis showed that Battelle’s polyol process is economical, at a 140 metric tons per day (MTD) polyol production scale. An attractive return on investment (ROI) at competitive pricing validates the process is ready for a pilot-plant demonstration. A scale-up plan is provided.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2022

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗

DOE OSTI2023

Social Acceptance of a Reduced-Footprint Synthetic Mooring System for Floating Offshore Wind Turbines in the Gulf of Maine

Engineers are looking to reduce the size of floating offshore wind mooring footprints to minimize conflict with other ocean users. To this end, the University of Maine (UMaine) received funding from the United States Department of Energy (DOE) to design, demonstrate, and validate a novel reduced-footprint synthetic mooring system for floating offshore wind turbines (FOWTs) that reduces impacts to fisheries and the levelized cost of energy. UMaine designed two mooring systems for the New England Aqua Ventus (NEAV) I demonstration project to quantify the technical, economic, and social impacts of a reduced-footprint hybrid mooring system. Specifically, a traditional catenary chain mooring system and a novel polyester rope-chain hybrid system were designed to the front-end engineering design level for this assessment. The National Renewable Energy Laboratory (NREL) was funded by DOE to help independently quantify the social and techno-economic impacts of the rope-chain hybrid mooring system designed by UMaine. This report focuses on NREL's assessment of the social acceptance of the reduced-footprint rope-chain hybrid mooring system and the conventional all-chain mooring system by competing users in the Gulf of Maine.

ENGINEERING,WIND ENERGY↗

DOE OSTI2024

End-Use Savings Shapes Measure Documentation: Window Film

This documentation focuses on a single end-use savings shape measure - window film. The window film studied in this analysis, called solar control film, is a passive retrofit solution for windows that does not involve window replacement. This type of film is composed of transparent, tinted, or metalized laminated polyester layers and can be attached to an existing window surface (either on the exterior or interior side of the window). The properties of the window film are designed to shift the thermal and optical performances of the overall glazing system in order to serve various needs the customer would have (e.g., heat, glare). While the practical goal of purchasing and installing a window film varies widely in the real market, this study only focuses on the goal of energy savings, and highlighting the corresponding emissions. Other important aspects that customers typically consider include visual comfort, privacy, aesthetics, ultraviolet protection, etc. Thus, in practice, customers often choose a window film product not only to save energy (or cost) but also to mitigate issues around glare, excessive light, daytime privacy, or inconsistent appearance of the building. Window film products that were modeled in this analysis significantly reduced the solar heat gain coefficient of the overall glazing system, resulting in better energy savings for buildings in hot climate regions. However, significantly reducing the solar heat gain coefficient that can block unfavorable heat during the summer can actually harm blocking favorable heat during the winter. By applying window films on a stock of buildings covering various load and weather conditions, this analysis highlights when (e.g., time of day) and where (e.g., geospacial location) we can save energy with window films.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗