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At least 235 records · Page 13

Semi-empirical quantum optics for mid-infrared molecular nanophotonics

Nanoscale infrared (IR) resonators with sub-diffraction limited mode volumes and open geometries have emerged as new platforms for implementing cavity quantum electrodynamics at room temperature. The use of IR nanoantennas and tip nanoprobes to study strong light–matter coupling of molecular vibrations with the vacuum field can be exploited for IR quantum control with nanometer spatial and femtosecond temporal resolution. In order to advance the development of molecule-based quantum nanophotonics in the mid-IR, we propose a generally applicable semi-empirical methodology based on quantum optics to describe light–matter interaction in systems driven by mid-IR femtosecond laser pulses. The theory is shown to reproduce recent experiments on the acceleration of the vibrational relaxation rate in infrared nanostructures. It also provides physical insights on the implementation of coherent phase rotations of the near-field using broadband nanotips. We then apply the quantum framework to develop general tip-design rules for the experimental manipulation of vibrational strong coupling and Fano interference effects in open infrared resonators. We finally propose the possibility of transferring the natural anharmonicity of molecular vibrational levels to the resonator near-field in the weak coupling regime to implement intensity-dependent phase shifts of the coupled system response with strong pulses and develop a vibrational chirping model to understand the effect. The semi-empirical quantum theory is equivalent to first-principles techniques based on Maxwell’s equations, but its lower computational cost suggests its use as a rapid design tool for the development of strongly coupled infrared nanophotonic hardware for applications ranging from quantum control of materials to quantum information processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental Fabrication of Porous Additive Manufactured Material

Nuclear industries can benefit from materials that can perform well mechanically and thermally in high temperature and corrosion environments. Functionally graded materials (FGM) are materials manufactured with complex spatial, structural, and chemical compositions, creating components predesigned with tailored microstructural and mechanical properties. Porosity-graded FGMs are designed to introduce pores into a component’s structure as a mechanism to increase bulk or surface material performance, such as stress accommodation and negative thermal conductivity. Additive manufacturing (AM) techniques such as laser energy net shape (LENS) and wire arc additive manufacturing (WAAM), excel in high energy density, point-to-point metal deposition, and present in combination with other combinatorial approaches, exciting methods to manufacture porous FGM components. This project is also examining plasma jet printing as another means for method evaluations for smaller scale graded components. This study explores AM FGM process parameters and combinatorial fabrication methodologies for stainless steel components functionally graded in porosity levels. Preliminary characterization results are provided to attest the feasibility of the combinational fabrication techniques.

36 MATERIALS SCIENCE↗

High Temperature Anode Recycle Blower for Solid Oxide Fuel Cell, Phase II (Final Report)

Broad commercialization of solid oxide fuel cells (SOFCs) requires anode offgas recycle blowers (ARCB) that are specifically designed for handling the challenging operating conditions presented by the SOFC process gases. Otherwise, they can be susceptible to frequent maintenance, low reliability, and short life. This report presents details of a DOE-funded Phase II effort conducted by Mohawk Innovative Technology, Inc. (MiTi®) for the development and testing of an oil-free, low cost, high-temperature centrifugal ARCB based on compliant foil bearing (CFB) technology for support of a 100 kW solid oxide fuel cell power plant. This Phase II builds on the results of a successful Phase I development project that resulted in the demonstration of a low TRL-6 prototype, shown in Figure 1. This Phase II final report presents design improvements over the Phase I prototype, presents the assembled test ARCBs, and discusses the advantages of this novel technology, particularly its long life and maintenance-free operation, which are derived from the use of CFBs. Also included are preliminary techno-economic analysis considerations for cost-effective deployment of the technology. The specific objectives of this project, as stated in the statement of program objectives (SOPO) were 1) to follow the methodology of design for manufacturing (or manufacturability) and assembly for implementing improvements identified as part of the Phase I effort with the purpose of reducing cost, enabling mass production, and facilitating the commercialization of a revised ARCB design, and 2) to fabricate four complete ARCB units based on the revised design and demonstrating their performance in both a laboratory setting and in an actual SOFC power plant. Execution of this SOPO would be supported by a number of technical tasks resulting in the fabrication and testing of the prototypes. To this end, MiTi continued the teaming relationship started during Phase I of the program with subcontracting partner FuelCell Energy, Inc. (FCE), which integrated (under a parallel effort funded by DOE Award DE-FE0026199) a modular 200 kWe SOFC power plant. MiTi and FCE coordinated to ultimately incorporate one of MiTi’s ARCB prototypes into one of the 100 kWe SOFC Modular Power Blocks (MPB) that constitute the core of FCE’s SOFC power plant for in-situ long-duration testing. Additionally, MiTi would explore the scalability and extendibility of the technology to other applications, as well as conduct a basic techno-economic analysis.

03 NATURAL GAS↗

Combining Experimental and Theoretical Techniques to Gain an Atomic Level Understanding of the Defect Binding Mechanism in Hard Carbon Anodes for Sodium Ion Batteries

Sodium ion batteries (NIBs) are an attractive alternative to lithium–ion batteries in applications that require large–scale energy storage due to sodium's high natural abundance and low cost. Hard carbon (HC) is the most promising anode material for NIBs; however, there is a knowledge gap in the understanding of the sodium binding mechanism that prevents a rational design of HC. This study tunes sucrose–derived HC via synthesis temperature then evaluates the structural, physical, and electrochemical properties. Neutron total scattering is used to generate structural models by fitting pair distribution functions (PDF) with a combination of molecular dynamics and reverse Monte Carlo methods. From this model, the number and type of structural features are identified, quantified, and correlated to the galvanostatic charge/discharge. A method of PDF “fingerprinting” binding sites using Na probe atoms is developed and analyzing these PDFs reveals an atomistic view of ion binding sites responsible for “defect” storage mechanisms. Combining these techniques results in an atomic–level study that provides a big picture of the Na–binding mechanism in NIBs, which allows for more precise tuning of the structure–property relationships in the future. Finally, the methodologies developed will also enable new strategies for the analysis of amorphous functional materials.

25 ENERGY STORAGE↗

Benchmarking Microscale Ductility Measurements (Final Report of the Project DE-NE0008799)

Conventional macroscale experimentation is generally considered to be straightforward with few limitations. Conversely, micro/nanoscale experimentation presents numerous challenges in loading device design, sample preparation and handling, as well as accurate understanding of grain size and local texture effects on recorded measurements. Despite these challenges, nanopillar compression, MEMs based micro-tension, and nanoindentation approaches have been able to provide fundamental contributions to the understanding of material behavior at small lengthscales. However, the overarching shortcoming of these micro/nanoscale experimentation approaches, is the inability to directly translate measurements evaluated at the nm and µm length scales (e.g., hardness) to macroscale tensile material behavior (i.e., elastic modulus, yield strength, and ductility). The objectives of the proposed study are, 1) to establish best practices for obtaining tensile microscale ductility measurements, and 2) to validate methodologies to for comparing microscale ductility measurements to macroscale ductility measurements. In order to achieve these objectives, a multi-lengthscale, multi-temperature testing protocol and simulation framework are executed first on copper as a model material to validate the following approach, and second on reactor grade Zircaloy-2. Experiments are conducted on specimens extracted from the same test piece to ensure nominally identical grain size and texture from specimens to specimen. Motivated by the need to isolate the contribution of size-effects on obtained mechanical property measurements, specimens are manufactured with thicknesses at the micro- (1-10 µm), meso- (10-100's µm), and macroscales (sub-sized ASTM E8). In-situ full-field deformation techniques (scanning electron microscopy (SEM) grid methods and optical DIC) are incorporated into testing at each specimen length-scale to capture plasticity localization and evolution. Experimental testing for all specimens is conducted at both room temperature and elevated temperatures to probe the role of thermal activation on plastic deformation accommodation processes. Simulation efforts focus on examining the mechanical behavior of microscale specimens using a finite element approach with explicitly resolved grain morphologies, and an embedded crystal plasticity model. The cost-efficient implementation method allows for the modeling of a statistically significant number of both real (i.e., digital twin) and generated microstructures to obtain an understanding of the interrelationships between specimen microstructure and geometric variables (grain size, texture, specimen geometry, etc.) on microscale mechanical behavior.

36 MATERIALS SCIENCE↗

Requirements Description of DASSH-F

This report reviews the modeling and simulation capabilities of Argonne National Laboratory’s DASSH code that is used in present reactor analysis activities. These capabilities will be used to establish the set of verification tasks necessary to verify DASSH for use on commercial projects. A similar approach was taken for the PERSENT, REBUS and DIF3D software packages. The DASSH program is a thermal analysis code designed to rapidly allow a reactor design engineer to obtain flow rates requirements that satisfy peak temperature constraints in the domain. DASSH is a follow-on development to the SE2-ANL software and SUPERENERGY-2 software that it is based upon. DASSH was designed to account for both neutron and gamma heating and is inherently connected to the GAMSOR part of the ARC suite of fast reactor analysis software. SE2-ANL is a developed piece of software from the 1980s while DASSH is a modern implementation with notable improvements in geometry handling. The most important upgrade of DASSH relative to SE2-ANL is that it can analyze multiple time points in a single run where SE2-ANL can only treat a single time point. This allows the user to understand the impact of and search the flow distribution for the entire operational period of a reactor design considering pressure drop, peak coolant and fuel temperatures, and thermal striping. DASSH has three input paths that have to be verified. The first input path builds the geometry and power distribution based upon the DIF3D model but ignores the gamma heating aspects of the problem. The second input path also builds the geometry from the DIF3D model but it takes the neutron and gamma heating distributions from GAMSOR. The third input path is to take the geometry and power distribution directly from user input (i.e. not coupled to DIF3D or GAMSOR). DASSH also has many built in correlations for material properties along with a user defined specification of the fuel, structure, and coolant properties. There are correlations for flow split, mixing, pressure drop, and heat transfer coefficients (subchannel rather than a direct methodology). In total, verification of DASSH will require an extensive testing to cover all possible user features of the software.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

FY23 status report on the development of new ASME Section III, Division 5 Class B rules

This report summarizes the work done in Fiscal Year 2023 on the development of the new American Society of Mechanical Engineers Boiler and Pressure Vessel Code, Section III, Division 5, Class B rules to address the gaps identified for high temperature reactor designs. The summary of the design-by-analysis strain limit evaluation and creep-fatigue damage assessment is presented. The proposed design-by-analysis creep-fatigue damage calculation approach uses a new elastic follow-up-based Isochronous Stress Strain Curve stress relaxation procedure. This approach captures the elastic follow-up generated due to interactions of components with adjacent components, supports, and other connections in the power plant. A set of sample problems are selected to validate the proposed design-by-analysis rules for creep-fatigue damage assessment. The proposed Class B rules are evaluated against the Class A elastic design rules, and the experimental data obtained from a family of Simplified Model Test based key-feature test results. The proposed Class B creep-fatigue damage assessment methodology yields conservative design cycles estimates compared to the experimental results.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Generation of localized reactor point kinetics parameters using coupled neutronic and thermal fluid models for pebble-bed reactor transient analysis

The systems analysis of anticipated operating occurrences and design basis accidents for pebble-bed reactor systems requires knowledge of neutron point kinetics equations (PKE) parameters. Typically, the generation of PKE parameters is performed in a global manner using standalone neutronics calculations, without the inclusion of thermal fluid distributions. We utilize Griffin and Pronghorn for generating global and local PKE parameters which includes the use of thermal fluid distributions to account for localized effects. This work establishes a methodology for calculating PKE parameters for a pebble bed reactor with a coupled neutronics/thermal fluids analysis. PKE parameters generated on a global and local basis are compared against a diffusion solve for a typical load-following transient. Locally-generated neutron kinetic parameters are able to reduce the maximum error in the transient power level from 5% to below 1.5%; along with this, bulk temperature errors were reduced from 12 K to 4 K.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Room Temperature Electrorefining of Rare Earth Metals from End-of-use Nd-Fe-B Magnets

Recovering rare earth elements (REE) from used permanent magnets, which contains about 30 wt.% of rare earth elements, has been persistent technological challenge. Current recycling methods relies on pyrometallurgical or hydrometallurgical processes which are energy- and chemical- intensive and not economically and environmentally viable for rare earth containing magnets. Enabling efficient and simplistic recovery and refining of REEs contained in End-of-Use (EoU) products, such as Neodymium-Iron-Boron (Nd-Fe-B) based magnets will play an important and complementary role in the total supply of REEs in the future. We designed a new electrochemical method and demonstrated a room temperature one-pot process that concurrently separates and electroplates REE from commercial Nd-Fe-B magnets. By establishing selective oxidation and reductive potential as electrochemical control parameter along with electrochemically compatible non-aqueous electrolyte system, we demonstrated selective electroleaching of lanthanides (Nd and Preseodymium (Pr)) from anode and concurrent plating as alloy at Pt cathode. The morphological and chemical evolution of the Nd-Fe-B magnets during electroleaching reveals the electrochemical stimuli and rate of dissolution depends on microstructural complexities of the Nd-Fe-B magnet. The concomitant electroplating process leads to Nd-Pr based alloy which can be used as raw metallic alloy for manufacturing new permanent magnet and other devices. Our study demonstrates a scalable separation and refining methodology, based on widely available organic electrolyte system and without any consumptive chemical use, for selective lanthanide recovery from waste magnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE Cold Climate Heat Pump Challenge Field Validation: Data Collection and Analysis Plan

This document details the data collection, storage, and analysis plan and methodologies for conducting the field validation portion of DOE’s Cold Climate Heat Pump (CCHP) Challenge. The study is focused on validating the in-field heating performance of prototypical CCHPs that have successfully demonstrated that they meet or exceed the Challenge specification in a laboratory setting. The units that have passed laboratory testing will be installed in real homes along with sensors and loggers for monitoring performance over an entire heating season. Data collected through monitoring will be cleaned and stored in a secure database. The data will be analyzed for calculating the key metrics defined by the Challenge including heating capacities at low outdoor air temperatures (below 32 °F), efficiency in terms of the Coefficient of Performance (COP), switchover temperatures and auxiliary heat staging. Demand Response (DR) capabilities will also be tested using specially designed DR events. In most cases, shoulder season and cooling season performance will also be determined and reported.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The Catalytic Activity of TiO 2 Toward a Multicomponent Reaction Depends on its Morphology, Mechanoactivation and Presence of Visible Light

Aims: Test the hypothesis that the catalytic activity of TiO2 nanoparticles towards a liquidphase or mechanoactivated multicomponent reaction can be tuned by visible light and the shape of nanoparticles. Background: Catalytic multicomponent reactions have been proven to be excellent synthetic approaches to a series of biologically relevant compounds including 2-amino-4H-benzo[b]pyrans. However, the potential photocatalytic activity and structural diversity of nanostructured catalysts remained underutilized in the design of new catalytic systems. Objective: Harness the photocatalytic potential and diverse morphology of TiO2 particles as catalysts for the liquid phase and mechanoactivated multicomponent organic reactions. Results: Catalytic activity of TiO2 nanoparticles towards multicomponent synthesis of 2-amino-4Hbenzo[ b]pyrans is increased by visible light. The nanorod-shaped TiO2 nanoparticles have shown substantially higher catalytic activity towards mechanoactivated multicomponent synthesis of 2- amino-4H-benzo[b]pyrans than their spherically-shaped counterparts. Conclusion: : An efficient methodology for the synthesis of 2-amino-4H-benzo[b]pyrans under ambient light condition has been developed using TiO2 nanorods (high aspect ratio anatase nanocrystals) as photocatalyst. This simple method furnished the corresponding terahydrobenzopyrans in high yields via three component reaction of aldehyde, malononitrile, and dimidone under solvent free reaction conditions at room temperature. The reaction takes 8-10 min at room temperature under ambient light condition and the catalyst can be reused multiple times. Utilization of light and the nanorod morphology of the catalyst through mechanoactivation has been applied for the -first time to the synthetic technique of multicomponent reactions. The synthetic procedures for 2-amino-4Hbenzo[ b]pyrans have been improved.

Thirumeni, Subramanian↗

Engineering Graphene-Ceramic 3D Composite Foams by Freeze Drying

A 3D graphene foam produced by the chemical vapor deposition (CVD) technique is recognized as an effective nanofiller material, as it does not agglomerate in the matrix. Though CVD facilitates pristine graphene foam production, the method poses limitations in developing large-scale 3D graphene composite foams as advanced engineering materials. In this paper, a freeze-drying (FD) process is used to produce a composite 3D foam, which is a mixture of graphene nanoplatelet (GNP) and a low-temperature co-fired ceramic (LTCC). The freeze-dried GNP-LTCC reticulated 3D composite foam has an average pore size ranging from 70 to 100 μm. Pore size is varied by regulating the heat transfer rate during the freezing process using a thermally conductive aluminum (Al) mold and a thermally insulating acrylonitrile butadiene styrene (ABS) mold. Computational thermal modeling is used to visualize the heat transfer and its effect on foam pore size. Subsequently, a freeze-dried GNP-LTCC composite foam is embedded into the LTCC matrix to form a hierarchical assembly by a spark plasma technique without compromising the 3D structure of the FD foam. This study established that a simple, eco-friendly, and scalable processing methodology can produce advanced graphene-based 3D composite foams as the future tailorable nanofillers for designing multimatrix materials.

36 MATERIALS SCIENCE↗

High-throughput ion irradiation of additively manufactured compositionally complex alloys

Several advanced nuclear reactor designs promise efficiency and safety improvements over the current reactor fleet but are limited by the current set of ASME code-qualified materials. Novel alloys including high-entropy alloys (HEAs), and more broadly compositionally complex alloys (CCAs), have shown promising irradiation-tolerance. However, the vast range of alloy compositions adds to an already time-consuming alloy development process. In this study, to accelerate the development of novel alloys for nuclear applications, a high-throughput (HTP) methodology has been employed. Additive manufacturing has been used to produce a compositional array of unary, binary, ternary, and quaternary alloys, including several CCAs, which span the Cr-Fe-Mn-Ni composition space. Additionally, the compositional array was homogenized at 1000°C for 24 hours and each sample was irradiated using 4-MeV Ni2+ ions at room temperature to a peak damage of 50 dpa, as estimated using SRIM, at the University of Wisconsin Ion Beam Laboratory. A custom XY stage was built to accommodate the large compositional array and half of each sample was masked during irradiation enabling both the irradiated and unirradiated properties of each alloy to be characterized side-by-side. Each alloy was characterized using X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and nanoindentation. CALPHAD simulations spanning the entire Cr-Fe-Mn-Ni composition space at 1000°C were performed to compare predicted equilibrium phases with phases identified experimentally from the unirradiated regions of each alloy. Nanoindentation measurements indicate radiation-induced hardening ranging from ~1-1.5 GPa in each of Cr-Fe-Mn-Ni CCAs, which is relatively insensitive to modest changes in alloy composition and comparable to hardening observed in neutron irradiated Cr-Fe-Mn-Ni CCAs in the literature. Overall, a substantial time savings was realized by employing HTP synthesis, irradiation, and characterization in this study compared to conventional techniques, the implications of which are discussed.

36 MATERIALS SCIENCE↗

Impact of Controlled Storage Conditions on the Hydrolysis and Surface Morphology of Amorphous-UO 3

The hydration and morphological effects of amorphous (A)-UO 3 following storage under varying temperature and relative humidity have been investigated. This study provides valuable insight into U-oxide speciation following aging, the U-oxide quantitative morphological data set, and, overall, the characterization of nuclear material provenance. A-UO 3 was synthesized via the washed uranyl peroxide synthetic route and aged based on a 3-factor circumscribed central composite design of experiment. Target aging times include 2.57, 7.00, 14.0, 21.0, and 25.4 days, temperatures of 5.51, 15.0, 30.0, 45.0, and 54.5 °C, and relative humidities of 14.2, 30.0, 55.0, 80.0, and 95.8% were examined. Following aging, crystallographic changes were quantified via powder X-ray diffraction and an internal standard Rietveld refinement method was used to confirm the hydration of A-UO 3 to crystalline schoepite phases. The particle morphology from scanning electron microscopy images was quantified using both the Morphological Analysis of MAterials software and machine learning. Results from the machine learning were processed via agglomerative hierarchical clustering analysis to distinguish trends in morphological attributes from the aging study. Significantly hydrated samples were found to have a much larger, plate-like morphology in comparison to the unaged controls. Predictive modeling via a response surface methodology determined that while aging time, temperature, and relative humidity all have a quantifiable effect on A-UO 3 crystallographic and morphological changes, relative humidity has the most significant impact.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adapting the Technology Performance Level Integrated Assessment Framework to Low-TRL Technologies Within the Carbon Capture, Utilization, and Storage Industry, Part I

With the urgent need to mitigate climate change and rising global temperatures, technological solutions that reduce atmospheric CO 2 are an increasingly important part of the global solution. As a result, the nascent carbon capture, utilization, and storage (CCUS) industry is rapidly growing with a plethora of new technologies in many different sectors. There is a need to holistically evaluate these new technologies in a standardized and consistent manner to determine which technologies will be the most successful and competitive in the global marketplace to achieve decarbonization targets. Life cycle assessment (LCA) and techno-economic assessment (TEA) have been employed as rigorous methodologies for quantitatively measuring a technology's environmental impacts and techno-economic performance, respectively. However, these metrics evaluate a technology's performance in only three dimensions and do not directly incorporate stakeholder needs and values. In addition, technology developers frequently encounter trade-offs during design that increase one metric at the expense of the other. The technology performance level (TPL) combined indicator provides a comprehensive and holistic assessment of an emerging technology's potential, which is described by its techno-economic performance, environmental impacts, social impacts, safety considerations, market/deployability opportunities, use integration impacts, and general risks. TPL incorporates TEA and LCA outputs and quantifies the trade-offs between them directly using stakeholder feedback and requirements. In this article, the TPL methodology is being adapted from the marine energy domain to the CCUS domain. Adapted metrics and definitions, a stakeholder analysis, and a detailed foundation-based application of the systems engineering approach to CCUS are presented. The TPL assessment framework is couched within the internationally standardized LCA framework to improve technical rigor and acceptance. It is demonstrated how stakeholder needs and values can be directly incorporated, how LCA and TEA metrics can be balanced, and how other dimensions (listed earlier) can be integrated into a single metric that measures a technology's potential.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Particle acceleration during classical phase transitions on a spherical lattice

Abstract When compressed, certain lattices undergo phase transitions that may allow nuclei to gain significant kinetic energy. To explore the dynamics of this phenomenon, we develop a methodology to study Coulomb coupled N -body systems constrained to a sphere, as in the Thomson problem. We initialize N total Boron nuclei as point particles on the surface of the sphere, allowing them to equilibrate via Coulomb scattering with a viscous damping term. To simulate a phase transition, we remove N rm particles, forcing the system to rearrange into a new equilibrium. With this model, we consider the Thomson problem as a dynamical system, providing a framework to explore how non-zero temperature affects structural imperfections in Thomson minima. We develop a scaling relation for the average peak kinetic energy attained by a single particle as a function of N and N rm . For certain values of N , we find an order of magnitude energy gain when increasing N rm from 1 to 6. The model may help to design a lattice that maximizes the energy output.

Bachmann, Aidan M. (ORCID:0000000294706404)↗

Development and Validation of a Simulation Testbed for the Intelligent Building Agents Laboratory (IBAL) Using TRNSYS

This paper documents the development and validation of a dynamic primary cooling and thermal storage system simulation testbed. The system simulation testbed, sIBAL, is based on the Intelligent Building Agents Laboratory (IBAL) at the National Institute of Standards and Technology (NIST), which is a research infrastructure and testbed for the development, evaluation, and demonstration of intelligent control algorithms. The sIBAL testbed developed in this project will serve as a virtual twin of the real facility for future control algorithm development. The details of the methodologies used to develop and validate the simulation testbed, which replicates the dynamic behaviors of the primary cooling and ice storage system in the IBAL facility, are presented. The simulation testbed was developed in TRNSYS using built-in component models and MATLAB functions to replicate the two water-cooled chillers, a thermal storage tank, pumps, valves and other components for four different operation modes. Experiments on IBAL components were designed and executed to generate experimental data for model development and verification of the simulation platform. The validation of the simulation results was carried out in two phases: 1) independent component simulations for the chillers and thermal storage tank, and 2) a combined testbed simulation of the entire hydronic system. Comparison of simulation results to the experimental data obtained from the IBAL facility showed errors within 1 °C for the temperatures outputs of both the chiller and the thermal storage model. The error is within an acceptable range for further intelligent control algorithms development. The findings from the study are summarized and presented along with areas where additional research is needed. In addition, data filtering procedures and model refinement measures utilized to improve the accuracy and accelerate the computation time of the simulation are presented.

cooling systems↗

Field Validation of Thermoelectric Generation System at Holcim Cement Plant in Alpena, Michigan

Executive Summary Project Background The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized energy-saving technologies in the industrial sector to help inform decisions to help accelerate their commercialization and deployment, as well as to help make industries more competitive. This ITV demonstration evaluated a thermoelectric generation (TEG) technology at a cement plant, aiming to reduce energy demand in the cement industry. A median cement plant consumes 5.73 million British thermal units per ton of clinker production (resulting in 0.838 metric tons of carbon dioxide [CO₂] emissions per ton of clinker) (Boyd and Zhang 2011, EPA 2021), equivalent to approximately 6.9 trillion British thermal units (TBtu) per year in energy consumption at a cement plant producing 3,300 tons of clinker per day.¹ Collaborating with Holcim, Advanced Thermovoltaic Systems (ATS) developed and deployed a pilot-scale thermoelectric power system to efficiently capture and convert waste heat to electricity. The system leverages the Seebeck effect to convert temperature differences on two sides of semiconductor cartridges into electrical power (ScienceDirect, n.d.). This generation is realized with minimal moving parts compared to existing waste-heat-to-generation solutions and allows capture from heat sources with temperatures as low as 150°C. This project aimed to validate a scalable solution applicable for capturing medium-temperature waste heat, including ambient losses from other high-temperature processes, and high-temperature sources less suitable for other waste-heat-to-power solutions. By recovering this otherwise wasted heat, this project intends to validate improvements to overall process efficiency through reduction in purchased electricity, thereby reducing operational costs while enhancing resiliency and competitiveness. Description and Scope This study evaluated the performance of a TEG system from ATS as a solution to convert waste heat into useful power at a Holcim cement plant in Alpena, Michigan. This plant is a fully integrated cement plant that has been operating since 1907. The facility operates continuously (24/7/365) with approximately 250 employees and five long dry kilns, yielding a total production capacity of 7,852 tons of cement per day (EPA 2023). Currently, the Alpena plant uses waste heat boilers to convert waste heat from the exhaust of each kiln into steam, which drives steam turbine generators. The ATS TEG is being evaluated for its potential to supplement the steam turbines by capturing the remaining lower grade heat. This technology is also being considered for other Holcim plants where steam turbines are not a viable option. ATS installed a pilot-scale TEG unit with an array of 582 individual thermoelectric semiconductor cartridges, of which 573 were operational. The cartridges are sandwiched between 48 hot plates and 49 cold plates. Each cartridge is designed to generate 20 watts (W) of gross power at a hot-side temperature of 240°C and cold-side temperature of 20°C. As such, the total gross generation capacity of the installed system is 11.5 kilowatts (kW) at design conditions. The system configuration for the evaluation was designed to prioritize convenience of installation and minimize disruption to production at the site, while ensuring that the heat required can be obtained for evaluating the TEG system at various operational conditions. To accomplish this, a portion of the steam supplied to Alpena’s steam turbine generation system was diverted to be used as the heat source for the TEG system, while water was supplied to the cold side of the system from nearby Lake Huron. This configuration was designed for the evaluation of the pilot-scale system to assess the performance at different conditions. A commercial-scale system will likely vary from the pilot system depending on typical configurations, including both scale and application. Future commercial applications of the ATS system would involve integrating the system into the exhaust from kiln preheaters, clinker coolers, or radiant heat capture from kiln shells for the heat source. For the cold source, a range of cooling solutions can be considered, including a mechanical cooling system, depending on the location and the application. To increase the generation capacity for commercial applications, the technology provider is working toward developing a commercial-scale TEG system, which would combine multiple TEG units (each similar in design to the pilot system) together. The scope of this evaluation includes the pilot-scale TEG system and all impacted equipment including pumps, controllers, and power handling equipment. Study Objectives The evaluation's goal was to assess the potential of the ATS TEG system to generate useful electrical power by capturing waste heat from cement production kilns. The objectives of this study are to evaluate and verify the following claims made by ATS regarding the pilot-scale system installed at the Holcim Alpena plant. The following design parameters and claims are also outlined in Table ES- 1 and Table ES- 2: • Gross Power: The thermoelectric system converts heat into power to create gross power, the total measured power generated by the system. The 573 active cartridge pilot-scale system is expected to generate 11.5 kW of gross power at the designed hot-side temperature of 240°C and cold-side temperature of 20°C. Power production is dependent on the temperature difference between the heat source (ultimately from the waste heat) and cold temperature supply source. • Net Power: The net power is the total usable power provided to the site by the TEG system after deducting parasitic power loads from the gross generated power. Supplementary equipment is required to operate the TEG system including pumps, controllers, and, in certain anticipated applications, mechanical cooling, which introduce parasitic loads to system operation. After deducting the parasitic loads from the gross power generation, ATS anticipates achieving a net power generation of 7.5 kW from the pilot-scale system. • Thermal Efficiency: The thermal efficiency is the percent of the total heat transferred to the TEG system that is converted to gross power. Historically, TEGs have a thermal efficiency of 2%–5% (DOE 2008). Prior industrial-scale TEG systems, such as the E1 TEG offered by Alphabet Energy, operated at an efficiency of 2.5% (Lamonica, 2014). ATS anticipates achieving an average efficiency of 4.8% or higher in converting heat energy to usable electricity. • Cartridge Performance: The TEG system comprises 573 active individual semiconductor cartridges, each of which generates a portion of the total power. Cartridge optimization and selection is an important design consideration for potential future TEG system design performance. Therefore, understanding the distribution of gross power and efficiency within the pilot system is vital to understanding what is achievable. At a design hot-side temperature of 240°C and cold-side temperature of 20°C, ATS anticipates a cartridge performance of 20 W of gross power per cartridge at an efficiency of 4.8% per cartridge. In addition to evaluating the claimed performance of the TEG pilot-scale unit, the study estimated the potential annual impacts of a scaled-up commercial system used to capture kiln waste heat over annual operations. The evaluation estimated the gross and net annual electric generation achievable by capturing heat from the two proposed tap-in points: the kiln exhaust and the clinker cooler exhaust; see Section 2.1 for details. Two use cases were examined: • Holcim Alpena: The Holcim Alpena site consists of long dry kilns with superheater boilers, which differs from the rest of Holcim’s cement plant portfolio and results in lower waste heat temperatures. The study estimates gross and net annual generation using the superheater boiler exhaust and clinker cooler exhaust, based on 2023 operational data. • Typical Installation: Common cement plants have preheater kilns with higher exhaust temperatures than Holcim Alpena across a range of production rates. The study estimates gross and net annual generation using the preheater exhaust and clinker cooler exhaust, with a sensitivity analysis to account for the typical range of preheater exhaust temperatures, clinker cooler exhaust temperatures, and clinker production rates. Methodology The evaluation methodology followed a measurement and verification (M&V) strategy based on the International Performance Measurement and Verification Protocol Option B through comprehensive measurements and analyses of the affected systems. Evaluation data was collected from March 9 to March 11, 2024, the test period of the pilot TEG system. During the test period, in coordination with the ITV team, the ATS team adjusted system operations to capture the range of variability expected for each of the variables pertinent to performance of the system. The methodology consisted of two parts: evaluating the performance of the pilot unit's TEG system and estimating the annual TEG impact in terms of gross and net power based on a given waste heat profile. First, the evaluation of the thermoelectric generation performance of the pilot unit relative to the claims was performed by analyzing the collected test data. Gross power of the pilot TEG system was directly measured. Net power was determined by deducting the measured parasitic power from the gross power. The gross power generation was compared to heat transferred to the system by the working fluid (which was heated by steam generated from the kiln waste heat) to calculate the thermal efficiency achieved by the system. Performance of individual semiconductor cartridges within the pilot array was also assessed in terms of measured gross cartridge power and calculated cartridge thermal efficiency. The second part of the evaluation estimated the annual TEG impacts in terms of gross power and net power (calculated from the difference between gross power and parasitic power). This analysis comprised development of mathematical regression models for gross power and parasitic power, with assessment of each model’s goodness-of-fit characteristics to ensure satisfaction of statistical requirements. The models predicted the gross power generation, the parasitic load based on the temperature difference between the hot working fluid and the cold-side fluid (cold water from Lake Huron) entering the system, the volumetric flow rate of the cold-side fluid at the inlet, and the volumetric flow rate of the hot working fluid at the inlet. The annual impact analysis considered a theoretical commercial-scale system sized to capture the available waste heat at a cement plant, consisting of linked pilot-scale units that receive heat from a theoretical gas-to-working-fluid heat exchanger. To estimate annual impacts at the Alpena plant, the gross power and parasitic power regression models were applied to the arrays in the theoretical commercial-scale system. The heat supplied to the unit was calculated based on the kiln run time, annual production, kiln exhaust waste heat, and clinker cooler waste heat derived from 2023 Holcim Alpena kiln operational data. Net power impacts were calculated by deducting the resulting parasitic power from the estimated gross power. Inputs for the model were generated from a combination of hourly data, assumed design considerations for TEG system scale-up from the pilot-scale unit, and assumptions regarding TEG system operations. This analysis was then used as the basis for estimating annual impacts of typical TEG installation at cement plants, by applying sensitivity analyses to key kiln operational characteristics including kiln preheater exhaust temperatures, cooler clinker exhaust temperatures, and plant daily production rates across a range of expected values. Project Results/Findings Table ES- 2 and Table ES- 2 provide a summary of the operating conditions and evaluation results compared to the stated claims from the technology provider. Key takeaways include: • Gross Power: The peak gross power achieved during the testing period was 10.0 kW, compared to the 11.5 kW expected for 573 active cartridges. The claimed gross power was associated with a target hot side of 240°C; however, the system only received a maximum hot-side mean plate temperature of 212°C during the testing period. • Net Power: The pilot-scale unit exceeded the claims for net power, achieving a peak of 7.7 kW net compared to a claim of 7.5 kW. One factor contributing to the higher achieved net power is the relatively high water pressure available through Lake Huron. The pilot TEG system did not require cold-side pumps during the test, whereas most installations would. This reduced the parasitic loads on the system, ultimately contributing to higher net power relative to the gross power. • Thermal Efficiency: The pilot-scale unit outperformed the claimed efficiency, achieving a peak system efficiency of 5.0% thermal efficiency compared to the stated 4.8%. • Cartridge Performance: To compare cartridge performance against claims, the study focused on the third day of testing, which aimed for conditions closest to the design specifications, with a hot side of 240°C and cold-side exit temperature of 6.4°–30°C. On this day, the mean gross power observed in the cartridges within the TEG array was 18.1 W/cartridge, and the peak performance was 34.7 W/cartridge. The estimated mean cartridge efficiency was 5.2%, and the estimated efficiency at peak gross cartridge power was 10%. The regression models developed for gross power generation and parasitic loads were used to estimate the generation impact for given heat input to the TEG from the working fluid (captured from the waste heat) and from the cold loop (Lake Huron) on an hourly basis for a year of operation. Based on this analysis, installation of a commercial-scale TEG system at the Holcim cement plant in Alpena, Michigan, with a waste heat exchanger of 0.85 effectiveness, would generate up to 391 kW of net power, translating to between 920,000 and 1,800,000 kilowatt-hours (kWh) in net electricity per year. Based on typical grid emissions for Alpena, this would avoid estimated net emissions by 752 metric tons of CO₂ annually.² The sensitivity analysis estimated that typical TEG system installations at cement plants could generate an average of 56–1,040 kW of net power, or between 488,000 and 9,110,000 kWh of net energy. This generation potential is most significantly affected by plant production rates and also influenced by preheater and clinker cooler exhaust temperatures. Applying the national average emission rate, typical commercial-scale installations at Holcim plants are projected to avoid between 182 and 3,401 metric tons of CO₂ annually per site. Table ES- 3 shows a summary of the estimated annual impacts.³ While parasitic loads are significant and vary by application, this analysis assumed the use of heating loop pumps and access to Lake Huron as a cold sink. This setup assumed no need for cooling loop pumps due to the available water pressure at the test site. Applications that require cooling towers or additional equipment are likely to experience higher parasitic loads. Therefore, the study’s estimates are most applicable to scenarios with similar parasitic load configurations—namely, access to a high-pressure cold sink. Applicability to other locations may be limited, as differing conditions could necessitate additional pumps and cooling systems, potentially impacting performance significantly.

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