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Results for “Polymer hydrolysis”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Magnetic resonance insights into the heterogeneous, fractal-like kinetics of chemically recyclable polymers

Moving toward a circular plastics economy is a vital aspect of global resource management. Chemical recycling of plastics ensures that high-value monomers can be recovered from depolymerized plastic waste, thus enabling circular manufacturing. However, to increase chemical recycling throughput in materials recovery facilities, the present understanding of polymer transport, diffusion, swelling, and heterogeneous deconstruction kinetics must be systematized to allow industrial-scale process design, spanning molecular to macroscopic regimes. To develop a framework for designing depolymerization processes, we examined acidolysis of circular polydiketoenamine elastomers. We used magnetic resonance to monitor spatially resolved observables in situ and then evaluated these data with a fractal method that treats nonlinear depolymerization kinetics. This approach delineated the roles played by network architecture and reaction medium on depolymerization outcomes, yielding parameters that facilitate comparisons between bulk processes. These streamlined methods to investigate polymer hydrolysis kinetics portend a general strategy for implementing chemical recycling on an industrial scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Diffusion-limited hydrolysis in polymeric materials

Polymer degradation under aggressive environmental stressors often develops heterogeneities due to diffusion-limited reaction phenomena. This is well established for diffusion-limited oxidation (DLO), which is known to occur for most polymeric materials at elevated temperatures but has been less summarized for the conditions of diffusion-limited hydrolysis (DLH). Here, an overview of hydrolysis for several materials and a computational model, analogous to the underlying equations for DLO, able to define this diffusion-reaction system is presented. A systematic study of the influence of various parameters, such as water diffusivity, reaction rate and order, and a more in-depth focus on residual isocyanate hydrolysis in a polymeric methylene diphenyl diisocyanate (pMDI) based polyurethane (PU) foam is given. For this system, we present experimental data for model ‘input’ parameters and discuss predictions for different conditions. We conceptually compare the behavior of diffusion-limited oxidation to that of diffusion-limited hydrolysis (DLH). With the mathematical framework and key material properties presented herein, any DLH phenomena following Fickian diffusion behavior can be understood, modeled, and predicted.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Circularity in Sequence-Controlled Copolyamides Enabled by Regioselective Enzymatic Hydrolysis

Sequence-controlled polymers enable precise control over macromolecular structures and function, but both their synthesis and end-of-life management remain fundamental challenges. Achieving high sequence fidelity is synthetically demanding, and conventional depolymerization methods lack regioselectivity, leading to irreversible loss of encoded molecular information and limiting polymer circularity. Enzymatic catalysis offers a potential solution by combining substrate specificity with selective bond cleavage. Here, we report the synthesis, characterization, and regioselective enzymatic depolymerization of poly- (X,AMA), a sequence-controlled copolyamide composed of alternating hexamethylenediamine−adipic acid (MA) and pxylylenediamine− adipic acid (XA) repeat units. Poly(X,AMA) was synthesized via solid-state polycondensation (SSP) of sequence-defined oligomers, enabling precise control over repeat-unit order. Polymer microstructure and sequence fidelity were confirmed by 13 C NMR spectroscopy and MALDI−TOF mass spectrometry. Comparison with a statistical copolymer analogue and Nylon-66 demonstrated pronounced differences in crystallinity, morphology, and thermal behavior arising from sequence control. Screening of 96 Nylon hydrolase homologues against poly(X,AMA) revealed strongly enzyme-dependent depolymerization profiles. While tetrad formation was generally favored, enzymes displayed pronounced sequence selectivity, preferentially releasing distinct sequence-defined tetrads XAMA or MAXA. SSP of sequence-defined tetrad MAXA produced a copolyamide with near identical monomer ordering as poly(X,AMA). Computational modeling of enzyme−substrate complexes identified structural features consistent with the observed regioselectivity. Together, these results establish selective enzymatic depolymerization as a viable strategy for the circular recycling of sequence-controlled polymers and provide a foundation for the rational engineering of enzymes for programmable polymer deconstruction.

Amides↗
NASA NTRS2005

Titania Deposition on PMR-15

The formation, degree of crystallinity and adherence of dense titania (TiO2) thin film coatings on a high-temperature polyimide resin (PMR-15) can be influenced by the chemical composition of the polymer surface. Furthermore, solution deposition conditions can be adjusted to provide additional control over the morphology and crystallinity of the titania films. Recipes for solution-based titania deposition that used a slowly-hydrolyzing titanium fluoride salt in the presence of boric acid as a fluoride scavenger allowed growth of films up to 750 nm thick in 22 h. By adjusting solution pH and temperature, either amorphous titania or oriented crystalline anatase films could be formed. Surface sulfonate groups enhance the adhesion of solution-deposited oxide thin film coatings. While most sulfonation procedures severely damaged the PMR-15 surface, the use of chlorosulfonic acid followed by hydrolysis of the installed chlorosulfonyl groups provided effective surface sulfonation without significant surface damage. In some cases, the oxide deposition solution caused partial hydrolysis of the polymer surface, which itself was sufficient to allow adhesion of the titania film through chelation of titanium ions by exposed benzoic acid groups on the polymer surface.

Meador, Mary B.↗
NASA NTRS1978

Polymers with complexing properties. Simple poly(amino acids)

The free amino (0.3 equiv/residue) and carboxyl (0.5 equiv/residue) groups of thermal polylysine increased dramatically on treatment with distilled water. The total hydrolysis of such a polymer was abnormal in that only about 50% of the expected amino acids were recovered. Poly (lysine-co-alanine-co-glycine) under usual conditions hydrolyzed completely in 8 hours; whereas, when it was pretreated with diazomethane, a normal period of 24 hours was required to give (nearly) the same amounts of each free amino acid as compared with those obtained from the untreated polymer. The amino groups of the basic thermal poly(amino acids) were sterically hindered. The existence of nitrogen atoms linking two or three chains and reactive groups (anhydride, imine) were proposed.

Roque, J. M.↗
DOE OSTI2023

Insight into the Structural and Emissive Behavior of a Three‐Dimensional Americium(III) Formate Coordination Polymer

Abstract We report the structural, vibrational, and optical properties of americium formate (Am(CHO 2 ) 3 ) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am 3+ ions linked by formate ligands into a three‐dimensional network that is isomorphous to several lanthanide analogs, (e. g., Eu 3+ , Nd 3+ , Tb 3+ ). Structure determination revealed a nine‐coordinate Am 3+ metal center that features a unique local C 3v symmetry. The metal–ligand bonding interactions were investigated by vibrational spectroscopy, natural localized molecular orbital calculations, and the quantum theory of atoms in molecules. The results paint a predominantly ionic bond picture and suggest the metal‐oxygen bonds increase in strength from Nd−O 5 D 1′ → 7 F 0′ emission band is observed and dominates the emission spectrum. This behavior is unusual and is attributed to the C 3v coordination environment of the metal center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Unveiling the catalytic mechanism of GTP hydrolysis in microtubules

Microtubules (MTs) are large cytoskeletal polymers, composed of αβ-tubulin heterodimers, capable of stochastically converting from polymerizing to depolymerizing states and vice versa. Depolymerization is coupled with hydrolysis of guanosine triphosphate (GTP) within β-tubulin. Hydrolysis is favored in the MT lattice compared to a free heterodimer with an experimentally observed rate increase of 500- to 700-fold, corresponding to an energetic barrier lowering of 3.8 to 4.0 kcal/mol. Mutagenesis studies have implicated α-tubulin residues, α:E254 and α:D251, as catalytic residues completing the β-tubulin active site of the lower heterodimer in the MT lattice. The mechanism for GTP hydrolysis in the free heterodimer, however, is not understood. Additionally, there has been debate concerning whether the GTP-state lattice is expanded or compacted relative to the GDP state and whether a “compacted” GDP-state lattice is required for hydrolysis. In this work, extensive quantum mechanics/molecular mechanics simulations with transition-tempered metadynamics free-energy sampling of compacted and expanded interdimer complexes, as well as a free heterodimer, have been carried out to provide clear insight into the GTP hydrolysis mechanism. α:E254 was found to be the catalytic residue in a compacted lattice, while in the expanded lattice, disruption of a key salt bridge interaction renders α:E254 less effective. The simulations reveal a barrier decrease of 3.8 ± 0.5 kcal/mol for the compacted lattice compared to a free heterodimer, in good agreement with experimental kinetic measurements. Additionally, the expanded lattice barrier was found to be 6.3 ± 0.5 kcal/mol higher than compacted, demonstrating that GTP hydrolysis is variable with lattice state and slower at the MT tip.

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

Solventless Dual‐Cure Liquid Resins Via Circular Use of Phthalic Anhydride for Recyclable Composite Applications

Abstract Fiber‐reinforced composites (FRCs) possess a remarkable strength‐to‐weight ratio, making them ideal light‐weighing alternative materials of metals used in automotive, aerospace, and outdoor equipment applications, but their recycling is challenging. Chemically recyclable thermoset polymers can enable fiber recovery and reuse; however, challenges remain in the separation and purification of depolymerized small molecules for efficient polymer recycling. To this end, a series of liquid resins for chemically recyclable polymer networks is designed based on phthalic anhydride, a widely produced and inexpensive chemical. The straightforward sublimation of phthalic anhydride is leveraged to enable a simple and efficient separation process for polymer recycling. To liquefy phthalic anhydride, five mono‐acryloyl‐phthalates are synthesized to obtain stable liquid resins together with phthalic diglycidyl ester. These liquid resins undergo dual‐cure reactions that comprise photopolymerization of acrylate and, subsequently, heat‐mediated epoxy‐acid polymerization reactions. These liquid resins exhibit moderate viscosities (2600–6400 cP @ 22 °C), fast curing, and robust thermomechanical properties (T g s from 71 to 116 °C). It is demonstrated that hydrolysis of the dual‐cured polymers completes within 2 h at 80 °C, and direct sublimation produces phthalic anhydride with 82% yield. This resin system is expected to provide a cost‐competitive, highly efficient platform for recyclable FRCs.

Polymer Science↗
DOE OSTI2023

Chemical structure–property relationships in nanocelluloses

Abstract Nanocelluloses, nanoscale cellulosic particles or fibrils, are an appealing class of nanomaterials with enormous potential for sustainable development. They have great promise to target some of the 17 Sustainable Development Goals outlined by the United Nations. Nanocelluloses are derived from the most abundant biopolymer in the world, cellulose, which have multiple hydroxyl groups on their surface, enabling a vast range of chemical modifications. The interplay between the chemical structure and physicochemical properties of nanocelluloses is crucial to engineering the next generation of green, functional nanomaterials. In this review paper, we provide a comprehensive account of the structure–property relationships in nanocelluloses, which may establish the basis for the design of precision bio‐based materials. Chemical modifications of nanocelluloses, including hydrolysis, oxidation, esterification, amidation, and polymer grafting, provide an array of chemical and physical properties that open opportunities in a diverse spectrum of applications. We review how chemical modifications affect the physicochemical properties of nanocelluloses, such as thermal stability, hydrophobicity, and dispersibility in nonpolar media. Understanding nanocellulose chemical structure–property relationships is integral to the development of sustainable material platforms based on the most renewable biopolymer on earth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Factors modulating the hydrolysis of Nylon-6,6 by a nylon hydrolase enzyme

The enzymatic hydrolysis of polyamides offers a promising approach to reduce the environmental impact of chemical recycling by enabling lower reaction temperatures, eliminating toxic organic solvents, and enhancing product selectivity. Achieving this goal will require increasing the low overall yield of enzymatic hydrolysis. In this work, we studied the mechanism of hydrolysis of commercial Nylon-6,6 polymer with a thermostable Nylon hydrolyzing enzyme and identified the substrate characteristics that influence the efficiency and deconstruction product yield. These results will guide the development of effective substrate pre-treatment methods to improve the yield of valuable oligoamide building blocks via enzymatic hydrolysis.

Bocharova, Vera [Oak Ridge National Laboratory (OR↗
DOE OSTI2024

Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar

A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goals of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O 2 (O 2 -enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pre-treatment oxidation (increasing H 2 O 2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. As a result, lignins recovered from the second stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than six-fold higher than for a typical hardwood kraft lignin, indicating these lignins could serve as a biobased polyol for a range of polyurethane applications.

09 BIOMASS FUELS↗
DOE OSTI2026

Understanding and Mitigating Stickiness in Biochar Produced through Acid Hydrolysis and Dehydration

Levulinic acid is a platform chemical with significant potential for conversion into a wide range of biobased chemicals and fuels. A common process for producing levulinic acid from lignocellulosic feedstocks involves acid hydrolysis and dehydration (AHDH), where hexose polymers are hydrolyzed into monomeric sugars and subsequently dehydrated to levulinic acid and formic acid in the presence of dilute sulfuric acid. However, scaling the AHDH process is challenging because of the formation of byproducts such as sticky biochar, which accumulates in continuous-flow reactors, reducing effective reaction volume and increasing process downtime. This study investigates the effect of a chemical preconditioning step on mitigating sticky biochar formation. Woody biomass was preconditioned at 170 °C with 0.26 wt % sulfuric acid for 30 min, resulting in substantial removal of hemicellulose and acid-soluble lignin. AHDH of these preconditioned solids produced biochar that did not adhere to reactor surfaces. TGA analysis confirmed that the chemical preconditioning step minimized interactions between hemicellulose-derived degradation products and lignin side chains, reducing sticky char formation. Additionally, the study observed a 6% higher yield of organic acids from softwood species compared to hardwoods, with bark content shown to negatively impact yield. These findings suggest that targeted preconditioning of lignocellulosic biomass can enhance reactor operability and improve organic acid production efficiency in AHDH processes.

biopolymers↗
DOE OSTI2024

Monitoring of Photovoltaic (PV) Performance and Degradation: Integrated Renewable Energy Systems (IRES) - PV Monitoring Task

The Integrated Renewable Energy System (IRES) testbed demonstration at the Pacific Northwest National Laboratory (PNNL) Sequim campus includes development of a suite of capabilities for tracking the performance of photovoltaic (PV) renewable energy components located on a floating platform (floating PV) and on a shoreline building rooftop. The marine environment represents potentially harsh and corrosive conditions for PV modules. Compared to terrestrial PV, potential concerns for offshore PV arising from high humidity and occasional contact with saltwater, marine wildlife, and aquaculture. These environmental factors can reduce electricity generation efficiency and increase the risk of electrical faults, polymer insulation or jacketing degradation and hydrolysis of the PV cell encapsulant materials. Offshore PV modules may also be exposed to lower temperatures and buoyant and vibrating motions with a floating platform. It is not clear how the long-term performance of floating PV will be affected by these factors. To understand expected energy generation through solar cells on a floating platform, monitoring of the performance of PV modules in the marine environment is needed. This report outlines a plan for long-term testing of IRES PV components utilizing resources of the PNNL Material Aging and Detection (MAaD) Science team and the Marine and Coastal Research Laboratory (MCRL). Equipment applicable for onsite testing and real-time monitoring of the PV performance associated with environmental conditions including temperature, solar irradiance, shading and soiling is included. In case of performance loss, equipment for fault detection, failure analysis, material testing, and further troubleshooting are also available. Through establishment of this capabilities, the enabling IRES project sets the stage for future research to advance off-shore and near-shore energy options for businesses and communities.

14 SOLAR ENERGY↗
DOE OSTI2022

The role of binding modules in enzymatic poly(ethylene terephthalate) hydrolysis at high-solids loadings

In nature, enzymes that deconstruct biological polymers, such as cellulose and chitin, often exhibit multi-domain architectures, comprising a catalytic domain and a non-catalytic binding module; the latter serves to increase the enzyme concentration at the substrate surface. This multi-domain architecture has been shown to improve the hydrolysis of poly(ethylene terephthalate) (PET) using engineered cutinase enzymes. Here, we examine the role of accessory binding modules at industrially relevant PET solids loadings necessary for cost-effective enzymatic recycling. Using a thermostable variant of leaf compost cutinase (LCC), we produced synthetic fusion constructs of LCC with five type A carbohydrate-binding modules (CBMs). At solids loadings below 10 wt%, the CBMs improve aromatic monomer yield from PET, but above this threshold, conversion extents up to 97% are reached with no added benefits from the presence of CBM fusions. This suggests that fusion constructs with the herein studied CBMs are not necessary for industrial enzymatic PET recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

The self-assembly of high-χ low-N block copolymers (BCPs) can give patterns with sub-10 nm full pitch, serving as a promising alternative to photolithographic methods. Here, in this work, we synthesized poly(solketal methacrylate)-block-polystyrene copolymers, PSM-b-PS, with various volume ratios of the two blocks. After hydrolysis of the PSM block into poly(glycerol monomethacrylate), PGM, the BCPs had both lamellar and cylindrical microdomain morphologies in the bulk phase and in thin films. In addition to our previously developed solid-state hydrolysis strategy involving trifluoroacetic acid vapor, we developed a new photoinduced solid-state hydrolysis using photoacid generators, PAGs, embedded within the polymer films. After exposure to UV followed by a postexposure baking or solvent vapor annealing, the BCPs transitioned from the disordered, phase-mixed state into laterally ordered cylindrical patterns. In comparison to linear BCPs that rely on a random copolymer layer to modify interfacial interactions with the substrate to promote an orientation of the microdomains normal to the interface, we found that the microdomains in bottlebrush multiblock copolymers oriented normal to the interface absent substrate modification due to the chain architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗