Engineering topics

Sinha, Sanjiv

Publications and source records attributed to Sinha, Sanjiv.

17 records

DOE OSTI2024

Hydrogel-Salt Hydrate Composite for Highly Stable Heat Energy Storage with Reduced Supercooling

Phase change materials (PCM) have potential for use in thermal energy storage in buildings, medical devices, and water heat pumps. Sodium sulfate hydrate (SSD) is appealing due to its high energy storage capability and affordability. However, SSD has issues including high supercooling (> 15°C) and low thermal cyclic stability. In this study, we introduced an ionic molecular nucleating agent that decreases the supercooling temperature to under 2°C. When this SSD was combined with a hydrogel, it maintained its thermal energy storage capacity for over 100 cycles without any decline. The success is attributed to the polymer confining the SSD crystals, preventing large-scale phase separation and the nucleating agent which resulted in nucleation of many small SSD crystals at small undercoolings rather than a small number of larger crystals. As a proof-of-application, we synthesized this composite at a kg scale and demonstrated its properties in a close to real-world demonstration.

chemical composition, thermodynamics↗

DOE OSTI2024

Identifying Molecular Scale Interactions of Nucleating Agents with Salt Hydrates for Thermal Energy Storage Applications

Latent heat based thermal energy storage is of interest as a method to mitigate and time-shift thermal load peaks and hence reduce energy demands for heating and cooling buildings. Notably, Glauber’s salt (GS) presents a good choice as a phase change material (PCM) for building applications because it has a melting point near room temperature (i.e., 32.4 °C), a large heat of fusion and energy density, and is low cost (~ $100/ton). However, there are several known limitations to using GS as a PCM, such as incongruent melting, high degree of supercooling, and formation of other hydration states, which renders GS unsuitable for practical use. Inorganic crystals acting as nucleating agents can avoid some of these issues with GS [1]. Understanding nucleation behavior through typical calorimetry experiments offers limited insight into the molecular-scale mechanisms. Here, we report isothermal titration calorimetry [2] to investigate the interactions between sodium sulfate salt and an organic nucleating agent - glycine. Our experiments provide qualitative and quantitative understanding of how glycine interacts with sodium sulfate across various temperatures. The findings offer insights into the nucleation onset temperature (24°C) and underscore the pivotal role of glycine's zwitterionic structure in facilitating nucleation. This preliminary work provides a foundation for subsequent exploration of nucleating agents that would be incorporated in different salt hydrate systems. 1. Purohit, B. K., and V. S. Sistla. "Inorganic salt hydrate for thermal energy storage application: A review." Energy Storage 3, no. 2 (2021): e212. 2. Velázquez-Campoy, Adrián, Hiroyasu Ohtaka, Azin Nezami, Salman Muzammil, and Ernesto Freire. "Isothermal titration calorimetry." Current protocols in cell biology 23, no. 1 (2004): 17-8.

calorimetry, nucleation & growth↗

DOE OSTI2024

Impact of Cooling Rate and Thermal Mass on Supercooling in a Salt-Hydrogel Complex for Thermal Energy Storage

Glauber’s salt is a promising phase change material for building thermal management because of its high latent heat, acceptable melting temperature of 32.3 °C for indoor air1,2. Despite these advantages, the practical application of Glauber’s salt in thermal energy storage systems is still challenging due to supercooling and phase segregation1–3. Here, we report the impact of temperature ramp rate and thermal mass on the supercooling of Glauber’s salt through the DSC and T-history experiment. The ramp rate effect was studied with a wide range of ramp rates in 1 to 10 °C/min in DSC and 1 to 4 °C/min in the T-history experiment. The thermal mass effect was investigated by comparing DSC and T-history experiment. The latent heat was also analyzed for different ramp rates and thermal mass conditions. The melting temperatures of Glauber’s salt from the two techniques were identical while freezing temperatures were different because of the thermal mass effect. During freezing in the T-history experiment, the latent heat was reduced by around 75% to the latent heat in melting due to supercooling and phase segregation. To overcome this bottleneck, we developed a novel hydrogel complex that reduces the supercooling and prevents phase segregation to maintain volumetric energy density for 100 cycles. Thermodynamic analysis accounting for composition shows that a higher salt composition can further enhance the volumetric energy storage density. For example, a 10% increase in the weight percentage of salt leads to about 50% enhancement in volumetric energy storage density. References: 1. D. R. Biswas, Solar Energy. 19, 99–100 (1977). 2. S. M. Hasnain, Energy Conversion and Management. 39, 1127–1138 (1998). 3. Byung Chul Shin, Sang Done Kim, P. Won-Hoon, Energy. 14, 921–930 (1989).

inorganic, thermodynamics↗

DOE OSTI2024

Method and apparatus for fabricating a hybrid tube

An apparatus for fabricating a hybrid tube includes a rotatable mandrel and a first housing configured to translate alongside the rotatable mandrel while dispensing a first strip to be helically wound about the mandrel. The first housing includes an angle adjustment mechanism to control a dispensation angle of the first strip. The apparatus also includes least one energy or adhesive source for bonding overlapping strip portions on the rotatable mandrel and forming the hybrid tube. The at least one energy or adhesive source is configured for translation alongside the rotatable mandrel.

Sinha, Sanjiv↗

DOE OSTI2024

Highly Ordered Eutectic Mesostructures via Template‐Directed Solidification within Thermally Engineered Templates

Template-directed self-assembly of solidifying eutectics results in emergence of unique microstructures due to diffusion constraints and thermal gradients imposed by the template. Here, the importance of selecting the template material based on its conductivity to control heat transfer between the template and the solidifying eutectic, and thus the thermal gradients near the solidification front, is demonstrated. Simulations elucidate the relationship between the thermal properties of the eutectic and template and the resultant microstructure. The overarching finding is that templates with low thermal conductivities are generally advantageous for forming highly organized microstructures. When electrochemically porosified silicon pillars (thermal conductivity < 0.3 Wm −1 K −1 ) are used as the template into which an AgCl-KCl eutectic is solidified, 99% of the unit cells in the solidified structure exhibit the same pattern. In contrast, when higher thermal conductivity crystalline silicon pillars (≈100 Wm −1 K −1 ) are utilized, the expected pattern is only present in 50% of the unit cells. The thermally engineered template results in mesostructures with tunable optical properties and reflectances nearly identical to the simulated reflectances of perfect structures, indicating highly ordered patterns are formed over large areas. This work highlights the importance of controlling heat flows in template-directed self-assembly of eutectics.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Thermal conductivity degradation due to radiation-induced amorphization in U 3 Si 2 : A pilot study

Here, in this study, we investigate the thermal conductivity of U 3 Si 2 amorphized by ion irradiation using 84 MeV 136 Xe ions at 190 °C. The suspended-bridge method was utilized to measure the thermal conductivity, allowing for a detailed analysis of the specimen while minimizing interference from other crystalline phases. Our results indicate that the thermal conductivity of amorphous U 3 Si 2 is significantly lower than that of unirradiated crystalline U 3 Si 2 . These findings are consistent with recent studies on in-pile-irradiated U 3 Si 2 samples that consider the effects of U 3 Si 2 amorphization, fission gas bubbles, and other impurities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Thermal Conductivity of a Novel Salt-Hydrogel Complex as a Phase Change Material for Building Thermal Management

Use of electricity for space heating, ventilation and air conditioning in buildings may be better managed through temporary energy storage. Compared with electrochemical storage, the levelized cost of thermal energy storage systems can be lower depending on geographical location and thermophysical properties [1]. In any phase change material (PCM), the rate of absorption and release of thermal energy increases with higher thermal conductivity [2]. However, leading PCMs like paraffin waxes have thermal conductivities on the order of 0.1 W/mK. Glauber’s salt, a salt hydrate, possesses a relatively high thermal conductivity but suffers from supercooling and phase segregation. Research has shown that polymer-based composites with salt hydrates can prevent phase segregation and limit supercooling over hundreds of cycles [3] though the thermal conductivity of the composite may be reduced leading to low energy storage rates. Here, we report thermal conductivity measurements on polymer hydrogels which are stable in solutions of Glauber’s salt. To measure thermal conductivity of soft gels, we use a 3-omega method [4] where heat flows bidirectionally through a substrate below and through a gel placed on top. This suits measurements of both gels and liquids unlike transient plane heat source or transient hot wire methods. We report measurements of thermal conductivity of salt-hydrogel complexes as a function of temperature, cross-linking and salt concentration. In addition, we present modeling of thermal conductivity of sodium sulfate solutions with available theories. We finally employ polarized optical microscopy to observe inside the transparent hydrogel networks, showing that precipitating crystals may influence thermal conductivity measurements for high salt concentrations. Our thermal conductivity results combined with enthalpy of phase change, mass density and specific heat are essential to accurately design thermal storage systems for energy-efficient buildings.

composite, thermal conductivity↗

DOE OSTI2023

Interpreting T-History Data on Supercooling and Phase Change Enthalpy of a Salt-Hydrogel Complex for Building Thermal Management

Phase change materials (PCMs) are promising materials for storing and discharging latent heat in buildings to regulate the thermal environment. Measurement of salt hydrate PCM thermal performance is often challenging because of supercooling and phase segregation. Though differential scanning calorimetry (DSC) has been widely used to measure thermal properties of various phase change materials, DSC uses milligrams of sample and is unrealistic for predicting large-scale materials performance. The T-history method [1], in contrast, handles higher volumes but the analysis typically requires a lumped capacitance assumption. Here, we report and analyze T-History data on a novel salt-hydrogel complex with high viscosity, that renders low Biot number sample preparation extremely challenging. We re-examine the standard T-history method and compared against DSC data in this complex material. We report details of an experimental setup, built with necessary additions to a controlled environmental chamber. We carefully examine the validity of the lumped capacitance assumption and suggest a modified analysis using a computational approach for reliable data. Experimental parameters such as ramp rate and temperature range of the environmental chamber are considered via computational modeling to understand the effect of ramp rate on supercooling [2]. Finally, we report thermal cycling experiments on the salt-hydrogel complex. Our modified approach to measuring supercooling and enthalpy of fusion at large scales is important in better understanding the performance of phase-change materials at scale for building thermal storage. References: [1] Marin, Jose M, Belen Zalba, Luisa F Cabeza, and Harald Mehling. “Determination of Enthalpy Temperature Curves of Phase Change Materials with the Temperature-History Method: Improvement to Temperature Dependent Properties.” Measurement Science and Technology 14, no. 2 (February 1, 2003): 184–89. https://doi.org/10.1088/0957-0233/14/2/305. [2] Safari, A., R. Saidur, F.A. Sulaiman, Yan Xu, and Joe Dong. “A Review on Supercooling of Phase Change Materials in Thermal Energy Storage Systems.” Renewable and Sustainable Energy Reviews 70 (April 2017): 905–19. https://doi.org/10.1016/j.rser.2016.11.272

thermodynamics↗

DOE OSTI2023

High Density Thermal Energy Storage by Highly Stable Glauber’s Salt Composites with Low Supercooling for Building-Scale Application

Phase change materials (PCM) are a promising candidate for thermal energy storage in building infrastructure, enabling grid-integrated peak load shaving by utilizing energy production in off-peak hours. Glauber’s salt (Na2SO4.10H2O, Sodium sulfate hydrate) are highly attractive due to their high energy storage capacity and low cost but Glauber’s salt suffers from long-standing challenges including high supercooling ( > 15oC) and low thermal cyclic stability, which is a major setback for practical building-scale energy storage applications. Here, we developed a unique ionic molecular nucleating agent for Glauber’s salt which reduced the supercooling temperature to less than 5oC. By combining this nucleated SSD with a polymer, phase segregation of salt hydrate for over 100 thermal cycles without degradation was achieved. Key was that the polymer confined the SSD crystals, preventing phase separation. In addition, we applied our stable Glauber’s salt composite in a miniatured building model and demonstrate that our PCM composite can be utilized for real-world building infrastructure.

additives↗

DOE OSTI2022

Measurement of Thermal Conductivity in a Supercooled Hydrogel-Salt Complex Near Its Phase Transition

Solid-liquid phase transitions, i.e. solidification processes, have applications in data storage, development of novel thermoelectric materials, cooling of microelectronic substrates and air conditioning condensers. Standard analyses of solidification (Stefan problem) assume constant thermal properties of the solid and liquid sides. It is not known how these properties change across the spatial transition interface, though most studies report a discontinuity in the solid and liquid properties through the transition temperature [1]. When the phase transition releases enthalpy, recent research has shown if the phonon or electron transport time is of the same order of magnitude as the time scale of the atomic transformation, this increases the heat capacity of the solid material at temperatures near the phase transition temperature [2]. A fundamental understanding of the phase transition may help shed light on the molecular origins of supercooling and spontaneous nucleation, which will help with applications involving them. We report studies of supercooling and nucleation of sodium sulfate decahydrate, a salt hydrate which is of recent interest in thermal storage, and of a hydrogel-sodium sulfate complex which shows limited supercooling. We will also report the measurement of their thermal properties during the phase transition process. This will be done with a hot-wire setup which produces small temperature changes of the order of ~1 C.

crystallization, phase transformation, thermal con↗

DOE OSTI2021

Thermal Conductivity Measurement of Microstructure in Irradiated Materials

Argonne National Laboratory is establishing additional capabilities for advanced techniques for accelerated experiment-based fuel material screening. A key supporting element is expanded capabilities for the characterization of irradiated samples, including establishment of the capability to measure irradiated fuel thermal conductivity at the micro-scale level. Argonne is collaborating with the University of Illinois at Urbana-Champaign (UIUC) to adopt the suspended bridge method to measure thermal conductivity of radiation-induced microstructures in nuclear materials directly. The initial phase of work to support thermal conductivity measurements of microstructure in irradiated materials at Argonne has been executed, and is summarized here. This report is intended to serve as a status update for this activity, summarizing work completed in FY20.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Ultralow Thermal Conductivity in Nanoporous Crystalline Fe 3 O 4

While there is no known fundamental lower limit to the thermal conductivity of a material, the lowest thermal conductivities are typically found in amorphous and strongly disordered materials, not highly crystalline materials. Here, we demonstrate a surprising nanostructuring route to ultralow thermal conductivity in a large-unit-cell oxide crystal (Fe 3 O 4 ) containing close-packed nanoscale pores. The electrical conductivity of this material reduces by a factor of 5 relative to dense v, independent of pore size. In contrast, thermal conductivity has a strong dependence on pore size with a factor of 40 of suppression relative to dense Fe 3 O 4 for 40 nm pores vs a factor of 5 for 500 nm pores. The matrix thermal conductivity of Fe 3 O 4 containing 40 nm pores falls below the predicted minimum thermal conductivity by a factor of 3. Finally, we attribute this to strong acoustic phonon scattering and intrinsically limited contributions to thermal conductivity from optical phonons with small dispersion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Multi-objective optimization of peel and shear strengths in ultrasonic metal welding using machine learning-based response surface methodology

Ultrasonic metal welding (UMW) is a solid-state joining technique with varied industrial applications. Despite of its numerous advantages, UMW has a relative narrow operating window and is sensitive to variations in process conditions. As such, it is imperative to quantitatively characterize the influence of welding parameters on the resulting joint quality. The quantification model can be subsequently used to optimize the parameters. Conventional response surface methodology (RSM) usually employs linear or polynomial models, which may not be able to capture the intricate, nonlinear input-output relationships in UMW. Furthermore, some UMW applications call for simultaneous optimization of multiple quality indices such as peel strength, shear strength, electrical conductivity, and thermal conductivity. To address these challenges, this paper develops a machine learning (ML)-based RSM to model the input-output relationships in UMW and jointly optimize two quality indices, namely, peel and shear strengths. The performance of various ML methods including spline regression, Gaussian process regression (GPR), support vector regression (SVR), and conventional polynomial regression models with different orders is compared. A case study using experimental data shows that GPR with radial basis function (RBF) kernel and SVR with RBF kernel achieve the best prediction accuracy. The obtained response surface models are then used to optimize a compound joint strength indicator that is defined as the average of normalized shear and peel strengths. In addition, the case study reveals different patterns in the response surfaces of shear and peel strengths, which has not been systematically studied in the literature. While developed for the UMW application, the method can be extended to other manufacturing processes.

42 ENGINEERING↗

DOE OSTI2020

Intrinsic thermal interfacial resistance measurement in bonded metal–polymer foils

Heat conduction through bonded metal–polymer interfaces often limits the overall heat transfer in electronic packaging, batteries, and heat recovery systems. To design the thermal circuit in such systems, it is essential to measure the thermal interfacial resistance (TIR) across ~1 µm to 100 µm junctions. Previously reported TIR of metal–polymer junctions utilize ASTM E1530-based two-block systems that measure the TIR by applying pressure across the interface through external heating and cooling blocks. Here, we report a novel modification of the ASTM-E1530 technique that employs integrated heaters and sensors to provide an intrinsic TIR measurement of an adhesively bonded metal–polymer junction. We design the measurement technique using finite element simulations to either passively suppress or actively compensate the lateral heat diffusion through the polymer, which can minimize the systematic error to ≲5%. Through proof-of-concept experiments, we report the TIR of metal–polymer interfaces made from DuPont’s Pyralux double-side copper-clad laminates, commonly used in flexible printed circuit boards. Our TIR measurement errors are <10%. We highlight additional sources of errors due to non-idealities in the experiment and discuss possible ways to overcome them. Our measurement technique is also applicable to interfaces that are electrically insulating such as adhesively joined metal–metal junctions and sputter-coated or welded metal–polymer junctions. Altogether, the technique is capable of measuring TIR ≳10 –5 m 2 KW –1 in bonded metal–polymer foils and can be tailored for in situ measurements in flexible electronics, circuit packaging, and other hybrid metal–polymer systems.

47 OTHER INSTRUMENTATION↗

DOE OSTI2020

Fouling modeling and prediction approach for heat exchangers using deep learning

In this article, we develop a generalized and scalable statistical model for accurate prediction of fouling resistance using commonly measured parameters of industrial heat exchangers. This prediction model is based on deep learning where a scalable algorithmic architecture learns non-linear functional relationships between a set of target and predictor variables from large number of training samples. Here, the efficacy of this modeling approach is demonstrated for predicting fouling in an analytically modeled cross-flow heat exchanger, designed for waste heat recovery from flue-gas using room temperature water. The performance results of the trained models demonstrate that the mean absolute prediction errors are under 10 –4 KW –1 for flue-gas side, water side and overall fouling resistances. The coefficients of determination (R 2 ), which characterize the goodness of fit between the predictions and observed data, are over 99%. Even under varying levels of measurement noise in the inputs, we demonstrate that predictions over an ensemble of multiple neural networks achieves better accuracy and robustness to noise. We find that the proposed deep-learning fouling prediction framework learns to follow heat exchanger flow and heat transfer physics, which we confirm using locally interpretable model agnostic explanations around randomly selected operating points. Overall, we provide a robust algorithmic framework for fouling prediction that can be generalized and scaled to various types of industrial heat exchangers.

42 ENGINEERING↗

DOE OSTI2020

Thermal conductivity measurement of the interaction layer between UMo and Al produced by high-energy heavy ion irradiation

In this work, we report the first direct thermal conductivity measurement results for Al-UMo interaction layer (IL), which is typically observed in UMo/Al dispersion fuel plates under irradiation. The investigated IL was formed by irradiating Al coated UMo substrate using 80 MeV iodine ions at 180 degrees C up to 3.03 x 10 17 ions/cm 2 fluence. Microstructural characterization indicated that the induced IL is amorphous with an approximately (U 0.8 ,Mo 0.2 )Al 5.3 stoichiometry, which is similar to that formed under in-pile irradiation. Focused ion beam (FIB) was used to prepare nine specimens of various lengths from the IL that could be suspended across a microfabricated device for thermal conductivity measurement. The measured thermal conductivity values of the IL were significantly lower than the values for both the original UMo fuel and the Al. The successful measurement of the Al-UMo IL provides valuable information for the development and qualification of UMo/Al dispersion fuels for research and test reactor conversion applications, and further demonstrates the promising capabilities of utilizing the suspended bridge method in nuclear fuel research.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Composite Structured Surfaces for Durable Dropwise Condensation

Dropwise condensation of steam on hydrophobic substrates has a 10X higher heat transfer coefficient compared to filmwise condensation. To promote dropwise condensation, low surface energy hydrophobic coatings (polymers) are typically utilized. The low intrinsic thermal conductivity (k < 1 W/(m · K)) of polymers, coupled with high heat transfer coefficient of dropwise condensation (100 kW/(m 2 · K)), necessitates that the coating be thin (< 1µm) in order to avoid reducing the overall heat exchanger conductance. However, thin polymeric films easily degrade. The two opposing requirements result in the need for optimization between the durability (thick coating) and the heat transfer (thin coating). To enable high thermal conductivity in thicker coatings, we develop metal-polymer structured surfaces. By using porous structures as inter-connected heat-conducting backbones that are filled with hydrophobic materials, we enable tuning of the coating effective thermal conductivity and surface energy. Three metal structures were studied; micro/nanowires, inverse opals, and sintered spheres. Heat transfer performance was calculated using three-dimensional finite element method simulations with two distinct boundary conditions; convection at the walls and isothermal walls. Interestingly, the overall conductance shows up to 40% difference depending on the boundary condition used in calculating the composite coating effective thermal conductivity. We use our model to predict the heat transfer performance as a function of metal fraction by volume and by surface area for condensation. By coupling our thermal simulations with a previously verified analytical model for predicting wetting behavior on heterogeneous surfaces, we propose a regime map to predict dropwise-to-filmwise transition. Furthermore, our work not only forms a starting point for the development of durable dropwise condensing surfaces, it identifies important considerations needed for computing effective thermal conductivity of composites.

42 ENGINEERING↗