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At least 73 records · Page 4

Ground radiation tests and flight atomic oxygen tests of ITO protective coatings for Galileo Spacecraft

Radiation simulation tests (protons and electrons) were performed along with atomic oxygen flight tests aboard the Shuttle to space qualify the surface protective coatings. The results, which contributed to the selection of indium-tin-oxide (ITO) coated polyester as the material for the thermal blankets of the Galileo Spacecraft, are given here. Two candidate materials, polyester and Fluorglas, were radiation-tested to determine changes at simulated Jovian radiation levels. The polyester exhibited a smaller weight loss (2.8) than the Fluorglas (8.8 percent). Other changes of polyester are given. During low-earth orbit, prior to transit to Jupiter, the thermal blankets would be exposed to atomic oxygen. Samples of uncoated and ITO-coated polyesters were flown on the Shuttle. Qualitative results are given which indicated that the ITO coating protected the underlying polyester.

Bouquet, Frank L.

Advanced Clothing Studies

All human space missions require significant logistical mass and volume that add an unprecedented burden on longduration missions beyond low-Earth orbit. For these missions with limited cleaning resources, a new wardrobe must be developed to reduce this logistical burden by reducing clothing mass and extending clothing wear. The present studies have been undertaken, for the first time, to measure length of wear and to assess the acceptance of such extended wear. Garments in these studies are commercially available exercise T-shirts and shorts, routine-wear T-shirts, and longsleeved pullover shirts. Fabric composition (cotton, polyester, light-weight, superfine Merino wool, modacrylic, cotton/rayon, polyester/Cocona, modacrylic/Xstatic, modacrylic/rayon, modacrylic/lyocell/aramid), construction (open knit, tight knit, open weave, tight weave), and finishing treatment (none, quaternary ammonium salt) are the independent variables. Eleven studies are reported here: five studies of exercise T-shirts, three of exercise shorts, two of routine wear Tshirts, and one of shirts used as sleep-wear. All studies are conducted in a climate-controlled environment, similar to a space vehicle's. For exercise clothing, study participants wear the garments during aerobic exercise. For routine wear clothing, study participants wear the T-shirts daily in an office or laboratory. Daily questionnaires collected data on ordinal preferences of nine sensory elements and on reason for retiring a used garment. Study 1 compares knitted cotton, polyester, and Merino exercise T-shirts (61 participants), study 2, knitted polyester, modacrylic, and polyester/Cocona exercise T-shirts (40 participants), study 3, cotton and polyester exercise shorts, knitted and woven (70 participants), all three using factorial experimental designs with and without a finishing treatment, conducted at the Johnson Space Center, sharing study participants. Study 4 compares knitted polyester and ZQ Merino exercise T-shirts, study 5, knitted ZQ Merino and modacrylic routine-wear T-shirts, with study 6 using only knitted polyester exercise shorts. No finishing treatment is used. Studies 4 and 5 use cross-over experimental designs, and all three studies were conducted aboard the ISS with six crew. Studies 4 and 6 were repeated on the ground with the same participants to learn if perception was affected microgravity. Study 7 is a longer-term, single-blind panel study of knitted routine-wear undershirts with at least 12 participants to assess tolerance to Merino by comparing it with a cotton/rayon blends, using a cross-over design, eliminating carryover effects with wash-out periods between shirts.

Orndoff, Evelyne

Enhancing Biopolyester Backbone Rigidity with an Asymmetric Furanic Monomer

Biobased furanic polyesters can exhibit performance advantages over petroleum-derived polyesters, primarily due to their rigid furan-containing backbones. Herein, we develop two strategies to polymerize methyl 5-hydroxymethyl furanoate to poly(5-hydroxymethyl furanoate) (PHMF), a furan-based polyester with even greater backbone rigidity than poly(ethylene furanoate). Thermal, spectroscopic, and computational investigations of PHMF alongside analogous furan-based and phenyl-based polyesters suggest that the high furan content of PHMF leads to its high glass transition temperature, slow crystallization kinetics, and low amorphous mobility. Molecular dynamics simulations suggest that while the backbone of PHMF is exceptionally rigid, its amorphous phase is denser than its phenyl analog due to noncovalent interchain interactions. Together, these results highlight how asymmetric furan-based monomers can modulate key properties in biobased polyesters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Engineering PHL7 for Improved Poly(Ethylene Terephthalate) Depolymerization via Rational Design and Directed Evolution

Enzymatic depolymerization of poly(ethylene terephthalate) (PET) has emerged as a promising approach for polyester recycling, and, to date, many natural and engineered PET hydrolase enzymes have been reported. For industrial use, PET hydrolases must achieve high depolymerization extent and exhibit excellent thermostability. Here, we engineered a natural PET hydrolase, Polyester Hydrolase Leipzig #7 (PHL7), through rational design and directed evolution using a high-throughput screening platform. Four new enzymes were engineered with enhanced properties compared with the parent enzyme, wild-type PHL7 (PHL7-WT), and other benchmark PET hydrolases, under the tested conditions. In bioreactors, the exemplary engineered enzyme, PHL7-Jemez, exhibited improved ability to depolymerize amorphous PET film compared with PHL7-WT at 2.9% and 20% substrate loadings, with 37% and 270% higher hydrolysis, respectively, after 48 h. This study develops several state-of-the-art PET hydrolases and demonstrates a directed evolution platform to engineer high-performance enzymes, which can accelerate enzyme discovery toward improved biocatalytic recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Thermodynamically leveraged solventless aerobic deconstruction of polyethylene-terephthalate plastics over a single-site molybdenum-dioxo catalyst

Here, we describe the solventless catalytic deconstruction of polyethylene-terephthalate (PET) under an aerobic atmosphere, mediated by an earth-abundant, low-cost activated carbon (AC)-supported single-site molybdenum-dioxo catalyst (AC/MoO 2 ). Catalytic amounts of AC/MoO 2 selectively convert waste PET into its monomer, terephthalic acid (TPA), within 4 h at 265 °C with yields as high as 94% under 1 atm air. Pure crystalline TPA product sublimes from the reaction hot zone, crystallizing on the reactor cold zone, thus avoiding the need for separation and purification steps. This process does not employ any hazardous/toxic reducing agents or solvents, and the catalyst can be recycled multiple times without loss of activity, rendering this process highly atom-efficient. According to computational and experimental mechanistic studies, the AC/MoO 2 catalyst mediates a thermoneutral metal-catalyzed β-scission step, followed by an exothermic step that converts the vinyl benzoate intermediate to TPA and acetaldehyde using trace amounts of moisture in the air. The formation of gaseous acetaldehyde makes the isolation of TPA from the reaction mixture facile and industrially favorable, especially since solvents are unnecessary. The present methodology is also extended to the deconstruction of other frequently used polyester plastics, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene furanoate (PEF), and operates equally well with post-consumer waste products. Notably, this process is also compatible with plastic mixtures of polyesters with polyolefins, polyamides, and polycarbonates, leading to the selective conversion of each polyester to the corresponding monomer, leaving the residual polymer unchanged and polyester-free.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Friction and morphology of magnetic tapes in sliding contact with nickel-zinc ferrite

Friction and morphological studies were conducted with magnetic tapes containing a Ni-Zn ferrite hemispherical pin in laboratory air at a relative humidity of 40 percent and at 23 C. The results indicate that the binder plays a significant role in the friction properties, morphology, and microstructure of the tape. Comparisons were made with four binders: nitrocellulose; poly (vinyledene) chloride; cellulose acetate; and hydroxyl-terminated, low molecular weight polyester added to the base polymer, polyester-polyurethane. The coefficient of friction was lowest for the tape with the nitrocellulose binder and increased in the order hydroxylterminated, low molecular weight polyester resin; poly (vinyledene) chloride; and cellulose acetate. The degree of enclosure of the oxide particles by the binder was highest for hydroxyl-terminated, low molecular weight polyester and decreased in the order cellulose acetate, poly (vinyledene) chloride, and nitrocellulose. The nature of deformation of the tape was a factor in controlling friction. The coefficient of friction under elastic contact conditions was considerably lower than under conditions that produced plastic contacts.

Miyoshi, K.

Durable Suit Bladder with Improved Water Permeability for Pressure and Environment Suits

Water vapor permeability is shown to be useful in rejecting heat and managing moisture accumulation in launch-and-entry pressure suits. Currently this is accomplished through a porous Gortex layer in the Advanced Crew and Escape Suit (ACES) and in the baseline design of the Constellation Suit System Element (CSSE) Suit 1. Non-porous dense monolithic membranes (DMM) that are available offer potential improvements for water vapor permeability with reduced gas leak. Accordingly, three different pressure bladder materials were investigated for water vapor permeability and oxygen leak: ElasthaneTM 80A (thermoplastic polyether urethane) provided from stock polymer material and two custom thermoplastic polyether urethanes. Water vapor, carbon dioxide and oxygen permeability of the DMM's was measured in a 0.13 mm thick stand-alone layer, a 0.08 mm and 0.05 mm thick layer each bonded to two different nylon and polyester woven reinforcing materials. Additional water vapor permeability and mechanical compression measurements were made with the reinforced 0.05 mm thick layers, further bonded with a polyester wicking and overlaid with moistened polyester fleece thermal underwear .This simulated the pressure from a supine crew person. The 0.05 mm thick nylon reinforced sample with polyester wicking layer was further mechanically tested for wear and abrasion. Concepts for incorporating these materials in launch/entry and Extravehicular Activity pressure suits are presented.

Bue, Grant C.

Astronaut Clothing for Exploration Missions

Astronaut clothes for exploration missions beyond low Earth orbit need to satisfy several challenges not met by the currently-used mostly-cotton clothing. A laundering system is not expected to be available, and thus soiled garments must be trashed. Jettisoning waste does not seem feasible at this time. The cabin oxygen concentration is expected to be higher than standard, and thus fabrics must better resist ignition and burning. Fabrics need to be identified that reduce logistical mass, that can be worn longer before disposal, that are at least as comfortable as cotton, and that resist ignition or that char immediately after ignition. Human factors and psychology indicate that crew well-being and morale require a variety of colors and styles to accommodate personal identity and preferences. Over the past four years, the Logistics Reduction Project under NASA's Advanced Exploration Systems Program has sponsored the Advanced Clothing System Task to conduct several ground studies and one ISS study. These studies have evaluated length of wear and personal preferences of commercially-available exercise- and routine-wear garments made from several fabrics (cotton, polyester, Merino wool, and modacrylic), woven and knitted. Note that Merino wool and modacrylic char like cotton in ambient air, while polyester unacceptably melts. This paper focuses on the two components of an International Space Station study, onboard and on the ground, with astronauts and cosmonauts. Fabrics were randomized to participants. Length of wear was assessed by statistical survival analysis, and preference by exact binomial confidence limits. Merino wool and modacrylic t-shirts were worn longer on average than polyester t-shirts. Interestingly, self-assessed preferences were inconsistent with length-of-wear behavior, as polyester was preferred to Merino wool and modacrylic.

Poritz, Darwin H.

Aqueous ionic liquid–mediated depolymerization of textile waste

Textile waste, dominated by polyester-cotton blends, largely evades recycling and ends up in landfills or incinerators. Here, we demonstrate an aqueous ionic liquid–mediated route for selective depolymerization of textile waste, including polyester and polycotton (polyester/cotton blend). Using aqueous cholinium lysinate ([Ch][Lys]), we depolymerized poly(ethylene terephthalate) (PET) textiles with over 95 % terephthalic acid (TPA) yields, comparable to virgin PET resin. Notably, colored fabrics showed no inhibitory effect from dyes. While protic ionic liquids such as ethanolammonium acetate showed limited efficiency, their precursor amine enabled near-complete PET conversion—ethanolamine promoted aminolysis with byproduct formation whereas butylamine achieved higher TPA recovery through combined hydrolysis and aminolysis. Importantly, polycotton blends achieved complete PET depolymerization with TPA yield above 85 % and preserved cotton. These results establish aqueous ionic liquids as efficient, selective agents for deconstructing polyester in blended textiles, offering flexible product and ionic liquid management pathways toward scalable and facile textile recycling.

Amines

Efficient secretion of a plastic degrading enzyme from the green algae Chlamydomonas reinhardtii

Abstract Plastic pollution has become a global crisis, with microplastics contaminating every environment on the planet, including our food, water, and even our bodies. In response, there is a growing interest in developing plastics that biodegrade naturally, thus avoiding the creation of persistent microplastics. As a mechanism to increase the rate of polyester plastic degradation, we examined the potential of using the green microalgaChlamydomonas reinhardtiifor the expression and secretion of PHL7, an enzyme that breaks down post-consumer polyethylene terephthalate (PET) plastics. We engineeredC. reinhardtiito secrete active PHL7 enzyme and selected strains showing robust expression, by using agar plates containing a polyester polyurethane (PU) dispersion as an efficient screening tool. This method demonstrated the enzyme’s efficacy in degrading ester bond-containing plastics, such as PET and bio-based polyurethanes, and highlights the potential for microalgae to be implemented in environmental biotechnology. The effectiveness of algal-expressed PHL7 in degrading plastics was shown by incubating PET with the supernatant from engineered strains, resulting in substantial plastic degradation, confirmed by mass spectrometry analysis of terephthalic acid formation from PET. Our findings demonstrate the feasibility of polyester plastic recycling using microalgae to produce plastic-degrading enzymes. This eco-friendly approach can support global efforts toward eliminating plastic in our environment, and aligns with the pursuit of low-carbon materials, as these engineered algae can also produce plastic monomer precursors. Finally, this data demonstratesC. reinhardtiicapabilities for recombinant enzyme production and secretion, offering a “green” alternative to traditional industrial enzyme production methods.

Science & Technology - Other Topics

Efficient secretion of a plastic degrading enzyme from the green algae Chlamydomonas reinhardtii

AbstractPlastic pollution has become a global crisis, with microplastics contaminating every environment on the planet, including our food, water, and even our bodies. In response, there is a growing interest in developing plastics that biodegrade naturally, thus avoiding the creation of persistent microplastics. As a mechanism to increase the rate of polyester plastic degradation, we examined the potential of using the green microalgaChlamydomonas reinhardtiifor the expression and secretion of PHL7, an enzyme that breaks down post-consumer polyethylene terephthalate (PET) plastics. We engineeredC. reinhardtiito secrete active PHL7 enzyme and selected strains showing robust expression, by using agar plates containing a polyester polyurethane (PU) dispersion as an efficient screening tool. This method demonstrated the enzyme’s efficacy in degrading ester bond-containing plastics, such as PET and bio-based polyurethanes, and highlights the potential for microalgae to be implemented in environmental biotechnology. The effectiveness of algal-expressed PHL7 in degrading plastics was shown by incubating PET with the supernatant from engineered strains, resulting in substantial plastic degradation, confirmed by mass spectrometry analysis of terephthalic acid (TPA) formation from PET. Our findings demonstrate the feasibility of polyester plastic recycling using microalgae to produce plastic-degrading enzymes. This eco-friendly approach can support global efforts toward eliminating plastic in our environment, and aligns with the pursuit of low-carbon materials, as these engineered algae can also produce plastic monomer precursors. Finally, this data demonstratesC. reinhardtiicapabilities for recombinant enzyme production and secretion, offering a “green” alternative to traditional industrial enzyme production methods.Graphical Abstract

Molino, João Vitor Dutra (ORCID:0000000324759807)

BOTTLE: Hybrid Chemical-Mechanical Separation and Upcycling of Mixed Plastic Waste

The main objective of this project is to develop a hybrid mechanical-chemical recycling technology for multilayered and laminated plastics. We aimed to separate and upcycle up to more than 80% of the two main constituents of such structures, polyolefins and polyesters, for a significantly lower cost and at higher energetic efficiency and much larger throughputs than chemical recycling. At the end of the project, the team was able to: a) Develop an extrusion-based separation technology that resorts to polyester depolymerizaton and extraction and allows for more than 90% of the polyester to be separated in the melt from the main polyolefin stream. b) Depolymerize the separated PET to more than 90%, which facilitates its posterior repolymerization and guarantees its retention in the polymer value-chain. c) Develop a zeolite-induced extrusion-based technology able to conduct continuous catalytic cracking of polyolefins, including highly contaminated PCR streams, at temperatures as low as 350 OC. d) Show, using LCA/TEA analysis that the two technologies are much more advantageous techno-economically and over the material’s life cycle than existing recycling technologies.

36 MATERIALS SCIENCE

The Triple Catalytic Action of Tertiary Nitrogen Catalysts in Recyclable Epoxy-Anhydride Thermosets

The thermosetting polymer matrix in fiber reinforced composites is an important component for energy related applications, such as the lightweighting of vehicles or their use in wind and waterpower turbine blades, due to their ability to provide superior adhesion, stiffness, and applicability to a wide range of manufacturing processes. Despite these benefits, today's thermosets are widely considered to be unrecyclable; thus, there is a large interest in redesigning these materials to be inherently recyclable so that energy intensive production of fibers and monomers can be circumvented, bolstering composite manufacture supply chains. Polyester covalent adaptable networks (PECANs) are one such promising alternative to the incumbent, nonrecyclable epoxy-amine thermosets. PECANs can be formed from the ring-opening co-polymerization (ROCOP) of epoxy-anhydride monomer mixtures and subsequent curing at mild temperatures to exhibit similar performance to conventional epoxies while also possessing unique dynamic chemistries along the ester-hydroxyl backbone that are capable of transesterification and thus reprocessability. While significant advancements have been made in formulating these materials for improved mechanical properties or optimizing solvolysis and reprocessing strategies, less attention has been placed on the impact of the residing amine catalyst used to generate the polyester network. In this work, we evaluated the triple-catalytic efficacy of 12 tertiary amines that act as a curing (bulk ROCOP), a transesterification (internal bond exchange), and a deconstruction (methanolysis) catalyst for PECAN thermosets. Specifically, we first distinguish between chain-growth and step-growth polymerization mechanisms for epoxy-amine and epoxy-anhydride mechanisms. We also utilized density functional theory (DFT) to estimate the basicity (pKb) of each catalyst. Of the tested catalysts, the ROCOP of the studied PECAN network can be completed between 95 and 247 min (at 80 degrees C), with variable gelation phenomena. Additionally, the stress relaxation (transesterification metric) efficiency of the tested PECAN networks with alternative embedded catalysts ranged from 95% to 15% reduction in stress after 5 h at 200 degrees C, and the depolymerization efficacy ranged from 2.5% to 9.8% deconstruction after 36 h at 130 degrees C. Overall, the nitrogen-based moieties were demonstrated to influence polymerization kinetics, catalyze the dynamic transesterification exchange mechanism, and aid in the solvolysis of the thermosets at end-of-life.

36 MATERIALS SCIENCE

Process innovations to enable viable enzymatic poly(ethylene terephthalate) recycling

Enzymatic depolymerization of poly(ethylene terephthalate) (PET) has received considerable attention for closed-loop polyester recycling. However, current approaches for enzymatic PET recycling face challenges to achieve commercial viability with lower environmental impacts compared with virgin polyester manufacturing. Here, in this study, we present multiple process innovations for enzymatic PET recycling that enable economic and environmental feasibility. We show that substrate amorphization through extrusion and quenching is energy-efficient and enables near-quantitative enzymatic conversion in 50 h. Using ammonium hydroxide for pH control and thermolysis of the isolated diammonium terephthalate salt reduces the acid and base consumption by >99%, lowering annual operating expenses by 74%. Fed-batch processing increased ethylene glycol concentration, leading to a 65% reduction in energy consumption for ethylene glycol recovery. These improvements were modeled in an optimal process, with recycled PET estimated to be US$\$$1.51 kg -1 relative to US domestic virgin PET at US$\$$1.87 kg -1 and eliminating key life cycle obstacles to scale this technology.

36 MATERIALS SCIENCE

Lignin-Derived Methoxyterephthalates for Performance-Advantaged Polymers and Plasticizers

Lignin-derived aromatic carboxylic acids can be produced from oxidative catalytic processes and are promising building blocks for performance-advantaged bioproducts that leverage their inherent heteroatom functionalities. Here, we synthesize 2-methoxyterephthalate and 2,6-dimethoxyterephthalate derivatives by electrochemical carboxylation of guaiacyl- and syringyl-derived lignin monomers obtained from the oxidative deconstruction of lignin. These methoxylated terephthalates are evaluated as comonomers in poly(ethylene terephthalate) (PET) and as plasticizers that could replace petrochemically-derived isophthalate and phthalate, respectively. Specifically, we copolymerize 2-methoxy- and 2,6-dimethoxyterephthalate with dimethyl terephthalate to form several PET copolymers, both of which enable the properties of PET to be tuned, with an incorporation beyond 25% producing amorphous polyesters. At 10 mol % loading in the copolymers, we demonstrate that the bioderived comonomers exhibit comparable behavior to isophthalic acid, a commonly used comonomer in PET, by lowering the crystallinity and melting temperature. Moreover, methoxyterephthalate esters (2-ethylhexyl and butyl) are compared to phthalate and terephthalate ester counterparts used as poly(vinyl chloride) (PVC) plasticizers. The bioderived plasticizers are comparable to the petroleum-derived incumbents in reducing the glass transition temperature and increasing the thermal stability of PVC. Furthermore, the dimethoxyterephthalic esters are expected to have an extended lifetime in the polymer matrix due to their lower volatility and lower diffusion coefficients calculated by molecular dynamic simulations. These results demonstrate that the isophthalate and phthalate components in polyesters and plasticizers, respectively, could be substituted with biobased methoxyterephthalate derivatives.

09 BIOMASS FUELS

Challenges and Opportunities in the Enzymatic Recycling of Nylons

Enzymatic depolymerization has the potential to contribute to nylon waste recycling. However, the implementation of a viable industrial process still lags far behind progress in enzymatic polyester recycling. Here we review the current biocatalytic nylon recycling landscape, highlighting biochemical, structural, and materials science barriers that currently limit depolymerization extents. We detail efforts to identify, engineer, and characterize new nylon depolymerases, where currently even the best biocatalysts rarely exceed ~1 wt% conversion of solid polymer to products. Based on our analyses, we suggest that limited substrate accessibility due to substrate crystallinity and hydrogen bonding, rather than intrinsic enzyme inefficiency or instability, is the primary bottleneck to enhanced depolymerization. Guided by successes in polyester enzymatic recycling, we outline a research roadmap combining nylonase engineering with polymer pretreatment, chemo-enzymatic cascades, and process analyses to accelerate development of viable enzymatic nylon recycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Development of a flameproof elastic elastomeric fiber

Various flexible polyurethane structures containing halogen were synthesized from polyesters derived from aliphatic or aromatic polyols and dibasic acids. Aliphatic halide structures could not be used because they are unstable at the required reaction temperatures, giving of hydrogen halide which hydrolyzes the ester linkages. In contract, halogen-containing aromatic polyols were stable and satisfactory products were made. The most promising composition, a brominated neopentyl glycol capped with toluene disocyanate, was used as a conventional diisocyanate, in conjunction with hydroxy-terminated polyethers or polyesters to form elastomeric urethanes containing about 10% bromine with weight. Products made in this manner will not burn in air, have an oxygen index value of about 25, and have tensile strength values of about 5,000 psi at 450% elongation. The most efficient additives for imparting flame retardancy to Spandex urethanes are aromatic halides and the most effective of these are the bromide compounds. Various levels of flame retardancy have been achieved depending on the levels of additives used.

Howarth, J. T.

Steady state thermal radiometers

A radiometer is described operating in a vacuum under steady state conditions. The front element is an aluminum sheet painted on the outer side with black or other absorptive material of selected characteristics. A thermocouple is bonded to the inner side of the aluminum sheet. That is backed by highly insulative layers of glass fiber and crinkled, aluminized Mylar polyester. Those layers are backed with a sturdy, polyester sheet, and the entire lamination is laced together by nylon cords. The device is highly reliable in that it does not drift out of calibration, and is significantly inexpensive.

Loose, J. D.