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

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Influence of Transition Metal Ion Contaminants on the Performance of Amine-Based Solid Sorbents in Direct Air Capture

Amine-functionalized solid sorbents are a class of sorbent materials proposed for direct air capture (DAC) of CO 2 , yet their long-term performance is susceptible to degradation under realistic operating conditions. Many amines are not thermodynamically stable in air, and amine sorbents oxidize while in use during DAC temperature swing adsorption processes. In this study, we investigate the role of transition metal ion contaminants, specifically Cu 2+ , Fe 2+ , and Ni 2+ , on the oxidative degradation of poly(ethylenimine) (PEI)-impregnated SBA-15 sorbents. By introducing metal ions via different modes mimicking both synthesis-related impurities and impurities derived from environmental exposure, we systematically evaluate sorbent stability after exposure to dry air at an elevated temperature. Thermogravimetric CO 2 uptake measurements reveal that even trace levels of Cu and Fe (as low as ∼4 ppm) can lead to measurable sorbent deactivation after oxidative aging, despite negligible loss in the performance of the control samples. In situ infrared, UV–vis, and X-ray photoelectron spectroscopies indicate that these metals catalyze radical-driven oxidation pathways, altering the chemical structure of the sorbent and accelerating degradation. Our findings underscore the need to account for trace metal contamination during DAC sorbent synthesis and deployment and highlight the importance of environmental contamination pathways.

CO2 capture↗
DOE OSTI2026

Impact of DMP-30 catalyst concentration on the degradation and kinetics of bisphenol A epoxy thermosets cured with linear amine hardener

Epoxy thermosets are a crucial component in carbon-fiber composites, serving as the organic binding matrix. Catalysts are commonly used in prepolymer formulations to accelerate curing of the thermosets. However, the impact of catalysts on the thermal stability, degradation pathways, and kinetics of the final thermoset is poorly understood. Here, in this work, Product-Specific Kinetics (PSK) analysis was utilized with isoconversional kinetics to provide a first look into the degradation kinetics of major pyrolysis pathways in bisphenol A (BPA) epoxy resins and determine the impact of altering catalysis concentrations on these kinetic pathways. Results revealed new insights into previously identified degradation pathways, provided evidence of multiple degradation pathways for some products, and showed that use of excess catalyst results in polymer network alterations and reduced thermal stability of the thermosets.

Bisphenol A↗
DOE OSTI2023

Pilot Testing of Amine-Based Solvent at Low-Rank Coal Fired Power System

Conference presentation for the 2023 International Freiberg Conference on Circular Carbon Technologies, Rotterdam, Netherlands, September 24–29, 2023. This presentation describes pilot testing of an amine-based CO₂ capture system at Coal Creek Station, examining solvent performance, system design, and operating conditions for a low-rank coal-fired power plant. The Mitsubishi Heavy Industries KM CDR (KS-1) process is assessed using pilot-scale data to inform capture efficiency, solvent condition, and integration considerations.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Sustainable Functional Epoxies through Boric Acid Templating

Thermoset polymers (e.g. epoxies, vulcanizable rubbers, polyurethanes, etc.) are crosslinked materials with excellent thermal, chemical, and mechanical stability; these properties make thermoset materials attractive for use in harsh applications and environments. Unfortunately, material robustness means that these materials persist in the environment with very slow degradation over long periods of time. Balancing the benefits of material performance with sustainability is a challenge in need of novel solutions. Here, we aimed to address this challenge by incorporating boronic acid-amine complexes into epoxy thermoset chemistries, facilitating degradation of the material under pH neutral to alkaline conditions; in this scenario, water acts as an initiator to remove boron species, creating a porous structure with an enhanced surface area that makes the material more amenable to environmental degradation. Furthermore, the expulsion of the boron leaves the residual pores rich in amines which can be exploited for CO 2 absorption or other functionalization. We demonstrated the formation of novel boron species from neat mixing of amine compounds with boric acid, including one complex that appears highly stable under nitrogen atmosphere up to 600 °C. While degradation of the materials under static, alkaline conditions (our “trigger”) was inconclusive at the time of this writing, dynamic conditions appeared more promising. Additionally, we showed that increasing boronic acid content created materials more resistant to thermal degradation, thus improving performance under typical high temperature use conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Purification of Degraded Aqueous Piperazine by Ion Exchange and Carbon Treating

Amine purification by ion exchange and carbon treating has been performed for decades to maintain low solvent impurity levels in amines used in natural gas sweetening. The use of these purification methods to remove dissolved metal catalysts and other impurities from amines used in post-combustion carbon capture is less well known. This report presents batch experiments testing the equilibrium adsorption of impurities from degraded piperazine (PZ) onto activated carbon and various ion exchange resins. Compared to cationic exchange, anionic exchange was found to better remove catalytic Fe and UV active species, making it a better candidate for large-scale PZ purification. Carbon treating greatly outperforms anion exchange in the removal of UV active species, but the adsorbents’ difference is less pronounced for the removal of other impurities. Equilibrium adsorption was determined by the UV absorption of the PZ solution at 320 nm, and the results will show this may not be an accurate way to determine equilibrium. Further bench-scale experiments comparing ion exchange and carbon treating are necessary before advancing to larger-scale testing.

amine purification↗
DOE OSTI2022

Performance Advantaged Thermosets from Bioderived Amines: Benefits in Manufacturing, Performance, and End-of-Life

Biomass derived monomers can offer unique functionality, often in the forms of heteroatoms, that is not easily accessible by routine petrochemical routes. Importantly, many of these monomers offer the potential to replace the petrochemical monomers used in the manufacture of thermosets to enable expanded functionality and performance. In the present work, we leverage amine containing monomers that can be obtained via biological conversions in both epoxy and benzoxazine thermosets. These monomers have a wide degree of functionality available to them that augment the material properties. In the case of benzoxazines, monomers that contain both an amine and carboxylic acid are used and the presence of the carboxylic acid leads to an acceleration in cure kinetics and a dramatic reduction in cure temperature. For the epoxy thermosets, multifunctional amine monomers are used as a hardener and the properties of the resultant materials are found to scale with the spacing and identity between reactive centers. The amines can be further modified and reacted to produce a mixed network of triazines and epoxy-amines that enables the end-of-life degradation of these materials. Importantly, subsequent process analysis reveals that the use of bioderived amines can present dramatic reductions in both supply chain energy and GHG emissions while possessing a cost similar to their petrochemical counterparts. Overall, this work demonstrates the robust potential to use bioderived amines for performance advantaged properties.

bioderived monomers↗
DOE OSTI2023

Identifying impacts of process, precursors, and defects in metal halide perovskite solar cells

With efficiencies of halide perovskite solar cells stagnating over the last few years at values above 25% and approaching thermodynamic limits, focus must shift to ensuring stability of these devices over the long term. The overarching goal of this project was to understand the root causes of instability in halide perovskite solar cells. Our approach was rooted in fundamental scientific pursuits, determining at the molecular level those processes responsible for degradation of the metal halide perovskite system, either in the precursor ink, or in the solid state. We then used this understanding to show that degradation leads to midgap states in halide perovskite semiconductors, explaining loss in performance; also, this in-depth understanding allowed us to develop specifically targeted solutions to prevent these degradation mechanisms. These include guidance about amines in perovskite inks, solvents to use (and not to use), and impacts of Cs incorporation to perovskite inks and solids. Finally, we achieved our end-of-project goal and demonstrated an effective lifetime of a halide perovskite solar cell of 5000 h, including measurement of devices over 3000 h, amongst the longest in the field. Overall, this project has considerably pushed forward the science of perovskite degradation and sets examples and groundwork for future studies to enable halide perovskite solar cells to be a successful solar energy conversion technology.

14 SOLAR ENERGY↗
DOE OSTI2023

Evaluating degradation of CO 2 adsorbents in flue gas from bioenergy with carbon capture and storage

For this work, the potential degradation of CO 2 adsorbents in Bioenergy with Carbon Capture and Storage (BECCS) was investigated through direct exposure to biomass combustion flue gas. Pre- and post-exposure characterization after 6–12 hours of exposure provided valuable insight into how common adsorbents would realistically perform in a BECCS process. The stability of zeolites and robust ZIFs was confirmed, but some unanticipated degradation mechanisms of less-stable MOFs and amine-based materials were also revealed, including pore fouling and chemical poisoning. The results emphasize the need for stability evaluations of adsorbents in comprehensive flue gas mixtures and suggest relationships between sorbent structure and degradation mechanism and extent.

09 BIOMASS FUELS↗
DOE OSTI2023

Gradient Amine Sorbents for Low Vacuum Swing CO 2 Capture at Ambient Temperature

The growing concerns over CO 2 emissions have led to the development of various methods for CO 2 capture. CO 2 capture by amine-based sorbents has been achieved by temperature (thermal) swing adsorption (TSA) process, pressure swing adsorption (PSA) process, and temperature pressure or vacuuming swing adsorption (TPSA or TVSA) process for CO 2 capture. Amine sorbents for energy-efficient TSA, PSA, VSA, TPSA or TVSA CO 2 capture should possess a capability which allow adsorbed CO 2 to desorb and amine sorbent to be regenerated at low temperatures or low vacuums. Development of such amine sorbents would significantly decrease energy consumption and sorbent degradation during the regeneration step. The objective of this project is to develop a low vacuum swing adsorption (VSA) process for the capture of CO 2 from air. The focus is on the development of amine sorbent which allows CO 2 to adsorb in the form of weakly adsorbed CO 2 . The weakly adsorbed CO 2 species can be collected from the sorbent by applying a low vacuum at ambient temperature. Specifically, no heating (i.e., thermal energy) is needed for regeneration of amine sorbents. This novel sorbent allows VSA to be operated at ambient temperature without a significant energy demand. This process eliminates the energy-intensive heating and cooling process in temperature swing adsorption (TSA) process. Ambient temperature operation could prolong the lifetime of sorbent and minimize the maintenance cost. Extensive sorbent studies with in-situ infrared spectroscopy have revealed the modifications of conventional amine sorbents with additives can increase the fraction of weakly adsorbed CO 2 . The amine sorbents with loaded CO 2 can be regenerated in part by the following approaches: (i) mild heating to temperatures below 70 °C, (ii) flowing purging gas over modified amine sorbents at temperatures below 40 °C, (iii) vacuuming at pressure below 0.2 atm and temperatures below 40 °C. The performance of these modified amine sorbents has been tested in a 60 grams VSA unit at ambient temperatures. The results show that weakly adsorbed CO 2 which can be desorbed from modified amine sorbents with purging gas at 100 cc/min can also be evacuated at a vacuum of 1 psia at room temperature. A preliminary techno- economic analysis indicates the major cost of the VSA process with modified amine sorbents stems from the operation of vacuum pumps. Thus, developing an excellent sealing with minimum leakage for the VSA unit is the most critical task for further the development of this VSA technology.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Energy-Efficient Direct Air Capture System for High Purity CO 2 Separation

The primary objective of this project is to demonstrate the University of Cincinnati’s direct air capture (DAC) sorbent technology in a monolithic structure installed in a passive air contactor (PAC). The modified amine-based sorbent technology provides reduced heat of desorption and resistance to thermal and oxidative degradations for robust and long-term performances and cost effective sorbent management. During the project period, additional amine modifications were developed and a U.S./PCT patent application was filed.

42 ENGINEERING↗
DOE OSTI2021

Chemical Kinetics of the Autoxidation of Poly(ethylenimine) in CO 2 Sorbents

The oxidative degradation rates of a CO 2 sorbent composed of a mesoporous alumina impregnated with poly- (ethylenimine) (PEI) are measured under systematically varied conditions and a reaction rate law is created. Good agreement is shown between the rate of oxidation obtained via in situ calorimetric heat measurement during oxidative degradation reactions and the loss of CO 2 capture performance presented as amine efficiency (mol CO 2 /mol amine). PEI mass loss and elemental composition are tracked over the course of the reaction and used in conjunction with the oxidation rate measurements to shed insight into the oxidation reaction(s). These data, in combination with measurements of the heat of reaction, suggest a common reaction set across the range of temperatures, oxygen concentrations, and sorbent compositions tested. The data are consistent with the basic autoxidation scheme (BAS), the accepted mechanism of autoxidation of aliphatic polymers. We propose a lumped kinetic model to describe the oxidation reaction set and estimate an activation energy of 105 kJ/mol and an oxygen reaction order of 0.5–0.7 from the data accordingly. Furthermore, these parameters can be incorporated into process cycle models to estimate the material lifetime, a critical uncertainty in the deployment of DAC technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Assessment of Long-Term Degradation of Adsorbents for Direct Air Capture by Ozonolysis

Porous adsorbents are a promising class of materials for the direct air capture of CO 2 (DAC). Practical implementation of adsorption-based DAC requires adsorbents that can be used for thousands of adsorption–desorption cycles without significant degradation. We examined the potential degradation of adsorbents by a mechanism that appears to have not been considered previously, namely, ozonolysis by trace levels of ozone from ambient air. We focused on amine-appended metal–organic frameworks, specifically amine-functionalized Mg 2 (dobpdc), as a representative DAC adsorbent. Estimates based on the number of amine sites in these adsorbents and the ozone concentration in air suggest that degradation by ozone may be relevant over thousands of adsorption–desorption cycles if reactions with adsorbed ozone are fast. We used density functional theory calculations to estimate reaction rates for amine groups and carbon–carbon double bonds in amine-functionalized Mg 2 (dobpdc).

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

Evaluating Autoxidation Radical Scavengers and Additives to Enhance Aminopolymer Sorbent Stability

Solid amine sorbents have shown promise in the removal of ultradilute CO 2 from the atmosphere. Despite being a promising candidate material type for this application, these sorbents are prone to degradation during long-term exposure to environmental components such as CO 2 , O 2 , and H 2 O, with amine oxidation being a particularly challenging problem. In this study, we investigate the potency of different radical scavengers and additives in mitigating the degradation of a model poly- (ethylenimine) (PEI)/Al 2 O 3 sorbent under direct air capture (DAC)-relevant conditions. The results reveal that a 4,4′-bis(α,α- dimethylbenzyl)diphenylamine (BDDPA)-incorporated PEI/Al 2 O 3 sorbent showed the most resistance toward oxidative degradation at varying exposure times and BDDPA loadings under CO 2 -free air (21% O 2 /balance N 2 ) at 120 °C. Interestingly, under humid (∼43% relative humidity (RH) at 26 °C) and dry 0.04% CO 2 -air, the BDDPA/PEI/Al 2 O 3 sorbent showed enhanced sorbent stability both at 70 and 120 °C after 4.5 h of exposure. Under humid CO 2 -free air, at 120 °C, the antioxidant performance slightly declined (in comparison to the dry CO 2 -free air condition) but displayed a much higher stability than the pristine sorbent. Overall, the ability of BDDPA to inhibit sorbent degradation under dry and humid, CO 2 -free and CO 2 -containing (0.04%) air at intermediate (70 °C) and elevated (120 °C) temperatures is promising in prolonging sorbent stability and underscores the importance of performing accelerated oxidation studies in the presence of all species that are expected to be present in DAC processes to identify suitable stabilization treatments for sorbent materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Proposed synthesis of a linear poly-ethylenimine with hydroxyl pendants substituents at the adjacent carbon

The synthesis of a linear poly-ethylenimine with pendant hydroxyl groups bonded to backbone carbons adjacent to the backbone amine groups is investigated and compared to the conventional method of functionalizing branched poly-ethylenimine using epoxides for use in direct air capture of carbon dioxide. The addition of hydroxyl groups imparts stability against both oxidative degradation and the formation of urea by reducing the number of primary amines, while the novel method of bonding to the adjacent backbone carbon rather than directly to the amine is hypothesized to retain the higher capacity for carbon dioxide of secondary amines when compared to tertiary amines. We also expect that the hydroxyl substituents will impart stronger hydrogen bonding capabilities, resulting in stronger interactions between adjacent polymer chains and a subsequent decrease in mobility.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Moisture-Induced Structural Degradation in Methylammonium Lead Iodide Perovskite Thin Films

Methylammonium lead iodide (CH 3 NH 3 PbI 3 , MAPbI 3 ) belongs to the group of organic–inorganic halide perovskites (OIHPs) that exhibit exceptional electrical and optical behavior suitable for photovoltaic applications. However, improving its structural and chemical stability and robustness remains a challenge for OIHPs to be considered a feasible active material in optoelectronic devices. This is due to the fact that this material is very susceptible to degrade under various intrinsic and extrinsic factors. Therefore, it is crucial to understand the mechanisms through which MAPbI 3 undergoes chemical degradation under operating conditions such as a relatively humid environment. We present the structural characteristics of MAPbI 3 under working conditions that suggest the routes of phase segregation as a result of exposing to highly moist media. We use dark pulse discharge behavior and current–voltage (I–V) variations of MAPbI 3 under different moisture levels to investigate the nature of structural degradation in OIHPs. Here we show that while relatively lower levels of humidity (~60% RH) have a limited impact on the structural stability of MAPbI 3 , exposure to higher levels of moisture (~100% RH) results in the formation of PbI 2 and aqueous CH 3 NH 3 I, which fundamentally change the charge transport characteristics in MAPbI 3 . Our findings explain the ongoing debate on the presence of a threshold for the humidity that triggers irreversible structural transformation and leads to full degradation of MAPbI 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Carbon Fiber Reinforced Epoxy Vitrimer: Robust Mechanical Performance and Facile Hydrothermal Decomposition in Pure Water

Conventional carbon fiber reinforced thermosetting polymers (CFRPs) are neither recyclable nor repairable due to their crosslinked network. The rapid growing CFRP market raises a serious concern of the waste management. In this work, a viable method to develop a readily recyclable CFRP based on epoxy vitrimer is introduced. First, a self-catalytic epoxy prepolymer with built-in hydroxy and tertiary amine groups is designed, which upon reaction with an anhydride formed a catalyst-free epoxy vitrimer. The epoxy prepolymer is synthesized from a diamine and an excess of bisphenol A epoxy resin. The hydroxyls and tertiary amines of the epoxy prepolymer efficiently catalyze both curing and the dynamic transesterification of the crosslinked polymer without the need of a catalyst. Then, the epoxy vitrimer is used as the matrix resin to prepare CFRP. The resulting CFRP exhibited a tensile strength as high as 356 MPa. More interestingly, the matrix of the CFRP is efficiently degraded in pure water at above 160 °C. This is because the built-in tertiary amines catalyze the hydrolysis of the ester bonds of the crosslinked network. The simple method developed in this work provides a framework for the development of recyclable CFRP.

Liu, Tuan↗
DOE OSTI2022

Amine Oxidation Catalyzed by NO 2

Amine oxidation is a major risk in the deployment of amine scrubbing for CO2 capture from post-combustion flue gas. Oxidation probably occurs by dissolved oxygen at elevated temperature, Fe(III)/Fe(II) shuttling between the absorber and the stripper, and by NO2 in the absorber. Amine selection, dissolved oxygen removal, and solvent reclaiming mitigate oxidation due to dissolved oxygen and iron shuttle mechanism, but not by NO2. This work examines piperazine (PZ) oxidation by NO2 in a bench-scale high gas flow reactor (HGF). PZ is an effective second-generation solvent with high CO2 capacity, fast capture rate, good thermal stability, and good resistance to oxidation. Flue gas typically contains 0.5–5 ppm NO2 and 10–100 ppm NO. NO2 at 1 ppm in the flue gas appears to cause significant amine oxidation in pilot plant testing. PZ solution can easily absorb NO2, and it is hypothesized that NO2 can catalytically oxidize PZ through free-radical propagation. The issue may not be solved by a NO2 pre-scrubber since the coexistence of NO and O2 in the flue gas will keep producing non-negligible amounts of NO2 in the ductwork and the absorber after the NO2 incoming with the flue gas has been scrubbed. In addition, NO2 may not only oxidize PZ but also the intermediate degradation products, and it is unknown if the existence of dissolved iron influences the oxidation by NO2. Previous workers have also shown that NO2 is the stoichiometric source of nitrosamine. A comprehensive analysis of NO2 oxidation is needed to address solvent management and its health/environmental impact. The new high gas flow (HGF) reactor focuses only on the absorber environment and is simpler to interpret because it does not include oxidation at high temperatures and by dissolved metal catalysts from corrosion. This paper presents the results of HGF experiments and shows evidence to support a hypothesis of amine oxidation catalyzed by NO2, presents the synergic effect of NO2 and iron on amine oxidation, points out the different effects of NO2 in clean and degraded solvents, and demonstrates that NO2 not only can oxidize amines but also their degradation products.

NO2, iron, piperazine (PZ), solvent oxidation, sol↗