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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Enhancing Building Energy Efficiency through Advanced Sizing and Dispatch Methods for Energy Storage

Energy storage and electrification of buildings hold great potential for future decarbonization. However, there are several technical and economic barriers that prevent large-scale adoption and integration of energy storage in buildings. These barriers include integration with building control systems, high capital costs, and the necessity to identify and quantify value streams for different stakeholders. To overcome these obstacles, it is crucial to develop advanced sizing and dispatch methods to assist planning and operational decision-making for integrating energy storage in buildings. This work develops simple and flexible optimal sizing and dispatch framework for thermal energy storage (TES) and battery energy storage (BES) systems in large-scale office building. The optimal sizes of TES, BES, as well as other building assets are determined in a joint manner instead of sequentially to avoid sub-optimal solutions. The interaction between the sizing at the planning stage and hourly or sub-hourly dispatch at the operating stage is explicitly modeled. The solution is determined considering both capital costs in optimal sizing and operational benefits in optimal dispatch. Comprehensive assessments are performed using simulation studies to quantify potential energy, economic, and emission benefits by different utility tariffs and climate locations, to improve our understanding of the techno-economic performance of different TES and BES systems, and to identify barriers for adopting energy storage for buildings. Finally, the proposed framework will provide guidance to a broad range of stakeholders to properly design energy storage in buildings and maximizes potential benefits, thereby advancing affordable building energy storage deployment and helping us accelerating the transition towards a cleaner and more equitable energy economy.

Yu, Mingyung↗
DOE OSTI2025

Polylactic acid (PLA)-based multifunctional and biodegradable nanocomposites and their applications

Polylactic acid (PLA)-based nanocomposites are emerging as multifunctional, biodegradable materials, offering sustainable alternatives to petroleum-based plastics. This review examines recent advancements in PLA nanocomposites, focusing on enhanced mechanical strength, thermal stability, and biodegradability achieved through nanofillers like metallic particles, carbon-based materials, and ceramics. Techniques such as in situ polymerization, melt mixing, and electrospinning enable application-specific improvements. PLA's limitations, including brittleness and low barrier properties, are addressed to support diverse applications: in packaging (e.g., extended shelf life), biomedicine (e.g., degradable implants), and electronics (e.g., flexible devices). Despite challenges with filler dispersion and thermal resistance, continued innovations expand PLA's potential across multiple industries, contributing to a sustainable, circular economy.

Biodegradable polymers↗
DOE OSTI2026

Novel Modular Heat Engines with sCO 2 Bottoming Cycle Utilizing Advanced Oil-Free Turbomachinery

This report presents the thermal, mechanical, and electric machine design of a 27krpm rotating test rig aimed at reducing technical risks with hermetic oil-free super-critical carbon dioxide (sCO 2 ) turbomachinery. The test rig rotor system is based on a conceptual turbomachine design discussed that evaluates a sCO 2 waste heat recovery (WHR) unit for land-based gas turbines at natural gas (NG) compressor stations. The key novelty of the hermetic sCO 2 turbomachine concept is the utilization of additively manufactured CO 2 gas bearings and a CO 2 -immersed direct-drive permanent magnet (PM) electric machine. The previous effort on conceptual design identified 3 main technical risks, which included thrust bearing load capacity, rotordynamics, and thermal performance of the system. Therefore, key requirements of the test vehicle include the ability to test the rotor system in a 400psi (27.6 bar) hermetic CO 2 operating environment, apply up to 1,500 lbs (6.7 kN) of rotor thrust loads, capability to assess rotordynamics with radial gas bearings, inclusion of instrumentation to assess thrust bearing load capability, and flexibility for varying secondary cooling flows to confirm thermal model predictions. Design topics such as rotordynamics, bearing design, and electric machine design are addressed, while highlighting critical elements. In addition, additive build trials for Inconel 718 radial and thrust bearings were performed to prove the manufacturability of the bearing design concepts. The results of the design efforts yield a test rig concept with ability to operate at 27,000 rpm, apply thrust loads to 1,500 lbs, deliver CO 2 up to 800psi, and modulate cooling flows.

03 NATURAL GAS↗
DOE OSTI2023

Optimizing mixed cool thermal storage systems across a connected community

A high level of electric demand flexibility must be integrated into our building infrastructure to enable greater renewable energy penetration in the grid. In the U.S., 9% of electricity generated is used to cool buildings in a periodic manner, making this end-use an ideal target for active management through cool thermal energy storage (CTES) technologies. Historic uses for CTES are designed around central chilled water plants, but these systems cool less than 25% of U.S. commercial floorspace. Emerging technologies are under development to serve the many smaller distributed cooling systems, such as rooftop units (RTUs), and have the potential to add CTES to an additional 66% of cooled commercial floorspace. However, these unitary thermal storage systems (UTSS) lack the modeling and analysis tools to evaluate them in the future interactive grid context. Here, this study develops the modeling and optimization tools necessary to simultaneously examine central and distributed ice storage systems within the multi-building, connected community context. An integrated simulation-optimization workflow is created to allow for rapid customized analysis. Results demonstrate the energy and flexibility tradeoffs of various implementations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Numerical modeling and parametric study of a dual purpose underground thermal battery

We report integrating thermal energy storage with building energy systems can enable flexible building electric demands at buildings to help mitigate the mismatch between electricity supply and demand. A novel building heating and cooling system that integrates a dual-source heat pump with hybrid thermal storage named dual-purpose underground thermal battery (DPUTB) has been developed for reshaping building electric demands. The proposed DPUTB integrated geothermal heat pump system is an original innovation that enables Grid-interactive Energy Efficient buildings. This paper focuses on the study of the novel DPUTB. The DPUTB works as both a thermal storage tank (an inner tank) and a ground heat exchanger (an outer tank separated from the inner tank by the insulation material). High fidelity and computationally effective models are needed to predict the performance of the novel DPUTB. This study has developed a simplified dynamic model for the DPUTB according to heat transfer and energy conservation principles and validated it by using experimental data obtained from testing a small-scale DPUTB apparatus. A parametric study was conducted to identify a design that can achieve the target thermal storage performance of load shift and energy efficiency. The parametric study results show that the inner tank shell thermal conductivity and the phase change material's melting point are the two most influencing factors on the performance of the DPUTB. One single full-size DPUTB with the identified design could provide 1-ton cooling (3.51 kW) with the supply temperature lower than 11 °C for 4 hours in summer after being fully charged in 8 hours. The inner tank filled with phase change material is for cooling thermal storage as a latent tank in the design. However, its capacity can be as high as 60 MJ as a sensible water tank for heating storage in winter. In the future study, the DPUTB model will be incorporated into the dual-source heat pump system for evaluating the overall system performance of demand side management in the long term.

25 ENERGY STORAGE↗
DOE OSTI2022

Insights into Methodologies and Operational Details of Resource Adequacy Assessment: A Case Study with Application to a Broader Flexibility Framework

Assessing and maintaining resource adequacy (RA) is a core pillar of power systems. However, recent changes in the physical makeup of these systems and the conditions under which these systems must operate have yielded a renewed interest in the methods, metrics, and assumptions that underpin RA assessments. In this paper, we systematically explore a wide range of RA modeling dimensions, including: the objective function and level of operational detail in the underlying model formulation; the quantity (look-ahead) and quality (accuracy) of data that is available for making operational decisions within those models; and the physical configuration of solar photovoltaics (PV) with battery storage hybrid resources. We apply a set of probabilistic RA tools and production cost modeling tools to a realistic test system based loosely on a future Electric Reliability Council of Texas power system dominated by solar PV resources. Under the assumptions of our system and models, we find that multi-stage probabilistic assessments may provide a more robust evaluation of RA by capturing a wider range of operational and system interactions, but this comes at a computational cost of 1-2 orders of magnitude longer run time depending on the specific configuration. In addition, the information on thermal generator availability impacts RA performance by an order of magnitude more than solar resource forecasts, which is driven by the comparatively larger magnitude of thermal outages than solar forecast errors within our test system. Lastly, the flexibility provided by hybrid and other resources can help reduce system load-shedding event frequencies and enable the system to be more robust to inaccurate forecast information, and alternative hybrid inverter sizes can impact RA levels by 1-2 orders of magnitude. Our results point to the importance of a broader flexibility framework to describe the interaction between (1) flexibility "supply" from both physical resource capabilities and operational constraints considered in the modeling, and (2) flexibility "demand" from forecast errors, thermal generator outages, and other sources of uncertainty, as well as their RA impacts. Results are likely sensitive to the system buildout explored; future work could consider additional system configurations and conditions.

ENERGY PLANNING, POLICY, AND ECONOMY,POWER TRANSMI↗
DOE OSTI2023

A Simulation Framework for Analyzing the Impact of Stochastic Occupant Behaviors on Demand Flexibility in Typical Commercial Buildings

As one of the primary users of the electric grid, buildings and building equipment, including heating, ventilation, and air conditioning (HVAC) systems, can be leveraged to provide the flexible demand needed to balance the grid. Typical strategies to achieve demand flexibility are to reduce electricity use during peak or critical periods by shutting down equipment or relaxing system setpoints, which will inevitably impact the occupants’ comfort. When occupants feel uncomfortable, they may take actions to regain their comfort, and some of those actions (such as turning on a personal fan) may have a negative impact on meeting the demand response goal. Therefore, it is important to incorporate occupant behaviors into the assessment ofthe building demand flexibility potential. In this study, a simulation framework that includes simulation of zone thermal loads, an HVAC system, and occupant behaviors, was developed to investigate the impact of occupant behaviors on demand flexibility. A case study was conducted using a small office model from the U.S. Department of Energy (DOE) Commercial Prototype Building Models to simulate the building envelope and zone loads. An agent-based occupant thermal behavior model was adapted to forecast occupants’ thermal comfort and their resulting thermal behaviors. An artificial neural network (ANN) based airflow model trained from a computational fluid dynamics (CFD) model of the zone was adopted to better predict the ambient environment of each occupant. An air-source heat pump simulation model that was calibrated from a real two-stage air-source heat pump system was used as the HVAC system. A typical load shedding event during peak hours was studied. Repeated simulations were conducted to capture the stochastic effects of occupant behaviors. The interplay between the demand flexibility, occupant comfort and behavior were analyzed by evaluating key performance indicators, including the energy use, occupant discomfort duration, and occupant behavior duration during the peak period. The results suggest that this framework can be used to analyze typical commercial buildings and their HVAC systems in terms ofdemand flexibility potential under the impact of occupant behaviors.

Chen, Zhelun↗
DOE OSTI2020

A scalable crosslinked fiberglass-aerogel thermal insulation composite

Ceramic aerogels are attractive for thermal insulation due to its lightweight and low thermal conductivity, while it is indispensable to address the obstacle of its brittleness nature and large-scale manufacturing for building efficiency applications. The economical manufacturing of large-scale elastic thermal insulation aerogels has remained challenging. Herein, we report a universal manufacturing of the fiberglass reinforced aerogel composites where the architectured three-dimensional fiber networks with the cross-linked silica aerogel exhibit superinsulation and mechanical elasticity. These remarkable performances are obtained through in-situ cross-linking reaction between molecular assembly induced aerogel and fiberglass under ambient pressure drying environment, in which the interfacial interactions are verified from its infrared spectra. The resulting ultralight aerogel composite sheet exhibits a density of 0.1 g cm -3 , large strain recovery (>50%), and low thermal conductivity (0.0253 W m –1 K –1 ). Here, the thermal insulation aerogel composites shed light on the super-elastic aerogel manufacturing with scalability for energy saving building applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Grid Interactive Micro-Distributed Display Case

The goal of this project is to design, fabricate and validate the performance of an economically viable next-generation self-contained, refrigerated open vertical display case with integrated thermal storage that improves energy efficiency, enhances demand flexibility, uses an environmentally friendly refrigerant, improves human comfort

25 ENERGY STORAGE↗
DOE OSTI2022

Effects of edge-seal design on the mechanical and thermal performance of vacuum-insulated glazing

Although vacuum-insulated glazing (VIG) has been proposed as a promising solution towards developing energy-efficient buildings, VIGs have not become popular in the market due to several technical challenges including the complexity of the fabrication process. In particular, the edge-seal is a key component that significantly affects the thermal insulation and mechanical performance, and the development of edge-seal with adequate thermal insulation, mechanical strength, and reasonable processing cost is essential to overcome such technical issues in VIG. For this purpose, effects of edge-seal design parameters on the VIG performance should be identified. In this research, we analyzed the edge-seal for thermal transport as well as structural stresses to study the effects, and then identified and evaluated the material mixes for the edge-seal requirements. Here, the finite element simulations showed the significance of VIG corner calculation on overall thermal transmittance and the importance of seal conductivity below 1 W/m.K. The experiments with the flexible seals with different ratios of fine glass powder demonstrated that the measured shear strength values for the seal with less than 30% glass powder were more than 10 times larger than the calculated shear stress values. Based on these simulation and experimental results, a flexible sealant was developed using a proprietary mix of ceramic materials that meets the requirements of the designed VIG edge-seal, including structural as well as thermal stress resistance and a low conductivity. Moreover, the sealant is self-curing under atmospheric conditions, and thus it does not require costly inline process of laser curing or oven baking.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Building energy efficiency and load flexibility optimization using phase change materials under futuristic grid scenario

This work investigates the energy savings and load flexibility capacity of phase change material (PCM) integrated into building envelope under a future energy generation scenario, where 80% of the energy load comes from renewable sources. Using community-scale modeling, we first determine the net thermal storage required to fully manage the demand variability at a utility grid, and then using whole-building simulations we optimize operating parameters - such as PCM thickness, latent heat, interior setpoint profile, PCM distribution, and heat transfer coefficient - to determine the optimal conditions required for maximum energy reduction and load flexibility without compromising occupants' thermal comfort. The optimal PCM-integrated envelope proposed in this study can provide annual load flexibility up to 33.6% and annual energy savings up to 10.8% in a lightweight residential building located in Baltimore, MD. This study is relevant given the increasing contributions of renewable energy in the total energy generation mix, leading to a significant time-imbalance between peak energy demand and peak energy production. While thermal energy storage using PCM is a recognized technique, there is no known prior study dedicated to examining the thermal performance of PCM-integrated envelope under future energy generation scenarios. This study bridges the research gap by investigating a practical way to implement PCMs in the buildings and maximize the energy efficiency as well as load flexibility related benefits.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

Techno-Economic Analysis of Greenfield Geothermal Hybrid Power Plants using a Solar or Natural Gas Steam Topping Cycle

The relatively low generation costs associated with wind, solar PV, and natural gas power plants make it challenging for geothermal power plants to produce and sell the power that has the reliability and sustainability characteristics that are greatly needed in US power markets. This is especially true for geothermal resources with low to medium temperatures, which results in relatively low thermal efficiency and generation costs that are higher than those for wind, solar PV, and natural gas. This analysis evaluates solar thermal- and natural gas combustion waste heat recovery-based topping cycle hybridization of geothermal binary power plants. This approach provides several benefits that may allow geothermal power plants to generate power at more competitive costs. First, the addition of solar thermal energy or natural gas combustion waste heat input to a geothermal power plant provides additional heat input that can be converted to electrical power. Second, the temperature level of the heat obtained from concentrating solar collectors or natural gas combustion exhaust is higher than that of geothermal heat, which provides opportunities for improving the efficiency of the conversion of thermal energy to electrical power. Third, the ease with which solar thermal systems integrate with energy storage and the flexibility of natural gas means power generation can occur during peak demand periods.

14 SOLAR ENERGY↗
DOE OSTI2024

Grid Interactive Micro-Distributed Refrigerated Display Case

Open-vertical medium-temperature refrigerated display cases comprise nearly 50% of total case lineups in a typical supermarket, with more than 80% of their cooling load attributed to infiltration of warm and moist air from the surrounding space. The infiltration takes place across the air curtain system of the display case. While the air curtain acts as a thermal shield and as a cooling mechanism to maintain product temperature, it also entrains large amounts of heat and moisture from the adjacent space. Additionally, from food safety and quality standpoints, these fixtures are vulnerable to electric outages and traditionally cannot participate in load flexibility events. This paper describes key features of an innovative design of a self-contained, water-cooled, medium-temperature, open-vertical display case. The novel concept will eliminate the inefficient air curtain system and incorporate a hybrid radiant and low-airflow convective cooling design with a thermal-energy-storage-coupled heat exchanger integrated into the refrigeration circuit. The focus of this paper is on evaluating the thermal performance of the novel hybrid design in maintaining target product temperature. It presents thermal performance findings from thermo-fluid system modeling and robust state-of-the-art laboratory experiments used to validate those models. Load flexibility attributes from thermal energy storage are not discussed. A controlled-environment chamber at the National Renewable Energy Laboratory was leveraged to validate the thermal performance of the novel technology. Final results from bench-scale experiments indicate the proposed design maintained mean product temperatures within food safety guidelines.

commercial refrigeration↗
DOE OSTI2024

Techno-Economic Analysis of Greenfield Geothermal Hybrid Power Plants using a Solar or Natural Gas Steam Topping Cycle

The relatively low generation costs associated with wind, solar photovoltaic (PV), and natural-gas power plants make it challenging for geothermal power plants to produce and sell the power that has the reliability and sustainability characteristics that are greatly needed in U.S. power markets. This is especially true for geothermal resources with low-to-medium temperatures, which results in relatively low-thermal efficiency and generation costs that are higher than those for wind, solar PV, and natural gas. This analysis evaluates solar thermal- and natural-gas combustion waste heat recovery-based topping cycle hybridization of geothermal binary power plants. This approach provides several benefits that may allow geothermal power plants to generate power at more competitive costs. First, the addition of solar thermal energy or natural-gas combustion waste heat input to a geothermal power plant provides additional heat input that can be converted to electrical power. Second, the temperature level of the heat obtained from concentrating solar collectors or natural-gas combustion exhaust is higher than that of geothermal heat, which provides opportunities for improving the efficiency of the conversion of thermal energy to electrical power. Third, the ease with which solar thermal systems integrate with energy storage and the flexibility of natural gas means power generation can occur during peak demand periods. The hybrid cycles are compared to equivalently sized, co-located, independent geothermal, concentrating solar, and/or natural-gas power plants. The hybrid cycle tends to produce slightly more power than the standalone plants combined. However, the hybrid plant Levelized Cost of Energy (LCOE) is slightly higher than the LCOE of the combined standalone power plants for each of the case study locations investigated. Using the steam-topping cycle, organic Rankine cycle (ORC)-bottoming cycle hybrid plant design to combine a solar thermal resource and low- temperature geothermal resource (<120 degrees C) leads to a hybrid plant with a lower LCOE than a standalone geothermal-only system. Thus, hybrid plants may enable the economic development of geothermal resources in locations with low geothermal resource temperatures. However, in areas with higher geothermal resource temperatures (>120 degrees C), the geothermal-only plant has a lower LCOE than the hybrid cycle and thus could be developed without the need for solar heat addition. iv A geothermal-natural-gas reciprocating engine hybrid plant was evaluated for an Elk Hills, California case study location. The Elk Hills case study analysis indicates that when the natural-gas engine operates for more than 12 hours per day the hybrid plant can produce power at an LCOE lower than a standalone geothermal plant, and comparable to that of the standalone natural-gas reciprocating engine, while also reducing the carbon intensity of the power generated relative to the standalone natural-gas engine. This may represent a scenario in which the hybrid plant provides an opportunity for the deployment of a low-temperature geothermal resource that otherwise may have an LCOE too high to develop and operate as a standalone resource, while also reducing the carbon intensity of natural-gas generation sources. A "triple-hybrid" plant that combines natural gas, solar thermal, thermal energy storage, and geothermal was also investigated. A natural-gas combustion turbine (NGCT) is added to the geothermal-solar hybrid such that the hot exhaust gas from the gas turbine provides an alternative source of heat to the steam turbine of the hybrid cycle. Analysis results suggest that the triple-hybrid plant has a significantly higher energy generation and revenue than a standalone NGCT or the original geothermal-solar hybrid. The triple-hybrid design benefits most from using a smaller solar field so that the solar energy can be dispatched at the most valuable times available. The triple-hybrid plant also has a lower LCOE than the standalone NGCT. The triple-hybrid plant was evaluated making simple assumptions about the dispatch profile of the gas cycle, and more nuanced and realistic dispatching schedules should be analyzed in future work.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Machine learning-assisted ultrafast flash sintering of high-performance and flexible silver–selenide thermoelectric devices

Flexible thermoelectric generators (TEGs) have shown immense potential for serving as a power source for wearable electronics and the Internet of Things. A key challenge preventing large-scale application of TEGs lies in the lack of a high-throughput processing method, which can sinter thermoelectric (TE) materials rapidly while maintaining their high thermoelectric properties. Herein, we integrate high-throughput experimentation and Bayesian optimization (BO) to accelerate the discovery of the optimum sintering conditions of silver–selenide TE films using an ultrafast intense pulsed light (flash) sintering technique. Due to the nature of the high-dimensional optimization problem of flash sintering processes, a Gaussian process regression (GPR) machine learning model is established to rapidly recommend the optimum flash sintering variables based on Bayesian expected improvement. For the first time, an ultrahigh-power factor flexible TE film (a power factor of 2205 μW m -1 K -2 with a zT of 1.1 at 300 K) is demonstrated with a sintering time less than 1.0 second, which is several orders of magnitude shorter than that of conventional thermal sintering techniques. Further, the films also show excellent flexibility with 92% retention of the power factor (PF) after 10 3 bending cycles with a 5 mm bending radius. In addition, a wearable thermoelectric generator based on the flash-sintered films generates a very competitive power density of 0.5 mW cm -2 at a temperature difference of 10 K. This work not only shows the tremendous potential of high-performance and flexible silver–selenide TEGs but also demonstrates a machine learning-assisted flash sintering strategy that could be used for ultrafast, high-throughput and scalable processing of functional materials for a broad range of energy and electronic applications.

25 ENERGY STORAGE↗
DOE OSTI2025

System Analysis of an Internal Combustion Engine (ICE) - Solid Oxide Fuel Cell (SOFC) Hybrid Cycle

The variability of renewable energy sources poses challenges for reliable grid operation. Conventional thermal power sources, though reliable, often lack operational flexibility. Hybrid energy systems that integrate Solid Oxide Fuel cells (SOFC) with Internal Combustion Engines (ICE) offer a promising solution by achieving relatively higher efficiency and grid-following capability. This study investigates performance of a 100-kW pressurized SOFC-ICE hybrid cycle. In this configuration, unutilized SOFC fuel is used to drive the engine, with a turbocharger providing air supply and an external reformer generating syngas. System components were numerically modeled using MATLAB/SIMULINK for the SOFC and reformer, and EBSILON® for the ICE and balance of plant. Parametric studies varied fuel utilization (70-90%), reformer temperature (600 – 1000K), anode off-gas recirculation (0 – 70%), and current density (0.2 – 0.55 A/cm2). Results show that the SOFC and ICE operate as thermally independent topping and bottoming cycles, achieving peak efficiency of 62% under optimized conditions.

hybrid↗
DOE OSTI2021

Recent Developments in the Design of Vertical Borehole Ground Heat Exchangers for Cost Reduction and Thermal Energy Storage

Ground source (geothermal) heat pumps (GSHPs) can meet the thermal demands of buildings in an energy-efficient manner. The current high installation costs and long payback period limit the attractiveness of GSHP installation in the United States. Vertical borehole ground heat exchangers (VBGHEs), which are commonly used in GSHP systems, contribute most to the cost premium of GSHPs. Reducing the cost of VBGHEs could help increase market penetration of GSHP systems. This paper reviews recent developments for VBGHEs, including improvements in borehole heat transfer and borehole field layout, integration with thermal energy storage, and new design tools. Improvements in the borehole design and materials are more likely to be justified when the ground has high thermal conductivity. Integrating thermal energy storage can provide additional value to the GSHP system, especially when flexible electric demand at buildings becomes more valuable. Here, advanced design tools for VBGHEs that account for the thermal response of irregularly shaped borehole fields and that are more closely integrated with whole-building energy simulation programs may facilitate more innovations and optimization of GSHP system designs.

15 GEOTHERMAL ENERGY↗
DOE OSTI2023

Structure, Dynamics, and Hydrogen Transport in Amorphous Polymers: An Analysis of the Interplay between Free Volume Element Distribution and Local Segmental Dynamics from Molecular Dynamics Simulations

Polymers are attractive membrane materials owing to their mechanical robustness and relatively inexpensive fabrication. An important indicator of membrane performance are free volume elements (FVE): microporous void spaces created by the inefficient packing of bulky groups along the polymer chain. FVEs tend to degrade over time, as polymer chains reorganize irreversibly. While it is widely accepted that polymer flexibility has an impact on membrane transport properties, the molecular nature of this impact is still not well understood. By the establishment of a correlation between local chain dynamics and the distribution of free volume elements (FVEs), penetrant transport can be regulated more efficiently in amorphous polymer membranes. In this work, we implement all-atom molecular dynamics (MD) simulations to explore the relationship between chain dynamics and free volume in three polymers with different levels of backbone flexibility: polymethylpentene (PMP), polystyrene (PS), and HAB-6FDA thermally rearranged polymer (TRP). We construct these polymers at different temperatures and examine how temperature impacts the FVE distribution and segmental mobility. Our analysis shows that chain segments near FVEs have higher mobility compared with the atoms in the bulk; the extent of this difference increases with chain flexibility. Increasing the chain flexibility by increasing the temperature results in a broader FVE distribution. Rigid polymers such as TRP show the most robust FVE distribution and are not significantly affected by the temperature change. To capture penetrant diffusion through the polymer matrix, hydrogen is inserted and the diffusion is measured at different temperatures; hydrogen mobility is influenced by the FVE structure and overall mobility of polymer chains. Lastly, at low temperatures, hydrogen mobility is influenced by void distribution, while at high temperatures, polymer dynamics dictate hydrogen transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗