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Stabilizing a low temperature phase change material based on Glaubers salt

The aim of this research is to enhance the performance of Glauber's salt (sodium sulfate decahydrate, SSD) as a phase change material (PCM) for thermal energy storage applications, as well as for shipping of temperature-sensitive materials. The study investigates the effects of modifying SSD with potassium chloride (KCl) and ammonium chloride (NH 4 Cl) to achieve lower phase transition temperatures of between +6 °C and + 13 °C. Sodium polyacrylate (PAAS) is employed as a thickening agent to prevent phase separation, and borax is used as a nucleating agent to suppress supercooling. Various ratios of KCl:NH 4 Cl are tested, and the impact of PAAS concentration on phase segregation is explored. The results show that a 2 wt% concentration of PAAS effectively prevents phase separation. Samples with a KCl:NH 4 Cl ratio of 1:1.83 exhibit stable phase transition behavior and maintain latent heat values within the range of 130–140 J/g after 30 thermal cycles. Maintaining a total KCl and NH 4 Cl proportion of 10 wt% is crucial to achieve the desired lower melting temperature. As a result, the study highlights the significance of thermal cycling in improving the stability of the PCM. The optimized SSD-based eutectic PCM formulations hold promise for applications in the cold chain industry.

25 ENERGY STORAGE↗

Glauber’s Salt Composites for HVAC Applications: A Study on the Use of the T-History Method with a Modified Data Evaluation Methodology

Phase change materials (PCMs) can be utilized in buildings for peak load shifting in air conditioning systems, and the use of salt hydrate-based PCMs can reduce the cost of thermal energy storage devices. Glauber’s salt is an economical salt hydrate PCM with a melting point of around 32 °C. However, the desired melting range typically falls between 18 and 22 °C for building air conditioning applications. Although many researchers have characterized Glauber’s salt and its composites with modified melting points, enthalpy–temperature curves for composites of Glauber’s salt and NaCl are unavailable. In this study, we report the melting and solidification enthalpy–temperature curves for two different composites of Glauber’s salt and NaCl with a melting point of 21 °C obtained by the T-history method. Both composites contain NaCl to suppress the melting point, borax to reduce supercooling, and sodium polyacrylate as a thickener to enhance cyclic stability. The first composite with 12 wt.% NaCl demonstrated 139 kJ·kg−1 of latent heat of fusion, and the second composite with 9 wt.% NaCl demonstrated 171 kJ·kg−1. Both the composites have high volumetric energy densities compared to their organic counterparts with similar melting points.

Chemistry↗

Heat storage capability of a rolling cylinder using Glauber's salt

The rolling cylinder phase change heat storage concept was developed to the point where a prototype design is completed and a cost analysis is prepared. A series of experimental and analytical tasks are defined to establish the thermal, mechanical, and materials behavior of rolling cylinder devices. These tasks include: analyses of internal and external heat transfer; performance and lifetime testing of the phase change materials; corrosion evaluation; development of a mathematical model; and design of a prototype and associated test equipment.

Herrick, C. S.↗

Influence of Carboxymethyl Cellulose as a Thickening Agent for Glauber’s Salt-Based Low Temperature PCM

This work is focused on a novel, promising low temperature phase change material (PCM), based on the eutectic Glauber’s salt composition. To allow phase transition within the refrigeration range of temperatures of +5 °C to +12 °C, combined with a high repeatability of melting–freezing processes, and minimized subcooling, the application of three variants of sodium carboxymethyl cellulose (Na-CMC) with distinct molecular weights (700,000, 250,000, and 90,000) is considered. The primary objective is to optimize the stabilization of this eutectic PCM formulation, while maintaining the desired enthalpy level. Preparation methods are refined to ensure repeatability in mixing components, thereby optimizing performance and stability. Additionally, the influence of Na-CMC molecular weight on stabilization is examined through differential scanning calorimetry (DSC), T-history, and rheology tests. The PCM formulation of interest builds upon prior research in which borax, ammonium chloride, and potassium chloride were used as additives to sodium sulfate decahydrate (Glauber’s salt), prioritizing environmentally responsible materials. The results reveal that CMC with molecular weights of 250 kg/mol and 90 kg/mol effectively stabilize the PCM without phase separation issues, slowing crystallization kinetics. Conversely, CMC of 700 kg/mol proved ineffective due to the disruption of gel formation at its low gel point, hindering higher concentrations. Calculations of ionic concentration indicate higher Na ion content in PCM stabilized with 90 kg/mol CMC, suggesting increased ionic interactions and gel strength. A tradeoff is discovered between the faster crystallization in lower molecular weight CMC and the higher concentration required, which increases the amount of inert material that does not participate in the phase transition. After thermal cycling, the best formulation had a latent heat of 130 J/g with no supercooling, demonstrating excellent performance. This work advances PCM’s reliability as a thermal energy storage solution for diverse applications and highlights the complex relationship between Na-CMC molecular weight and PCM stabilization.

25 ENERGY STORAGE↗

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↗

High-Density, Low-Hysteresis Storage Using Hydrated Salts in Surface-Functionalized Hydrogels (Final Technical Report)

Nearly 70 years ago, Glauber’s salt was identified as a leading phase change material (PCM) in terms of its heat storage density (~2x paraffin), thermal conductivity (~1W/m·K), safety, availability and cost (~$\$$100/ton). However, the complex issues of supercooling and incongruent melting due to phase separation have prevented realization of the promise. The addition of thickeners and nucleating agents such as borax solve these issues but only over few cycles. This work aims to (a) resolve long-standing challenges with Glauber’s salt as a thermal storage material through a unique materials approach, (b) to characterize the new material’s properties that are relevant to performance and (c) to explore its incorporation into commercial water heaters. The materials concept involves encapsulating the salt in custom-designed, large-mesh hydrogels that enable breakthrough advances. Specifically, (1) the choice of mesh size and polymer chemistry control diffusion of salt/water and help to eliminate phase segregation. With the hydrogel itself occupying <10% volume, there is little loss in storage density compared to another encapsulation. (2) Specific nucleation centers that covalently tether to the hydrogel trigger heterogeneous nucleation, eliminating supercooling-associated hysteresis losses. The fact that they are spatially tethered, prevents the loss in performance over multiple freeze/thaw cycles (>100). We report extensive characterization of the hydrogel complex in terms of its storage density, freezing/melting temperature, cycling losses, rheological properties, aging and thermal conductivity. The novel material developed in this work is a significant advancement over the state-of-art. Finally, we investigate its potential as a thermal storage material for commercial/residential water heating and identify scenarios in which its deployment is advantageous.

25 ENERGY STORAGE↗

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↗

Fluctuation history of Great Salt Lake, Utah, during the last 13,000 years, part 2

Great Salt Lake level fluctuations from 13,000 yr B.P. to the present were interpreted by examination of shoreline geomorphic features, shoreline deposits, archeologic sites, isotopic data, and palynologic data. After the conclusion of the Bonneville paleolake cycle, between 13,000 and 12,000 yr B.P. the lake regressed to levels low enough to deposit a littoral oxidized red bed stratum and a pelagic Glauber's salt layer. A late Pleistocene lake cycle occurred between 12,000 and 10,000 yr B.P. depositing several beaches, the highest reaching an altitude of about 4250 ft (1295.3 m). The lake regressed after 10,000 yr B.P., only to rise to 4230 ft (1289.2 m) between 9700 and 9400 yr B.P. and then gradually lower at least 15 ft (4.5 m) or more. Lake levels fluctuated between 4212 and 4180 ft (1284 and 1274 m) for the next 4000 years. A late Holocene lake cycle, constrained by radiocarbon ages between 3440 and 1400 yr B.P., is reported at a highest static level of 4221 ft (1286.5 m). After a lake level drop to altitudes ranging between 4210 and 4205 ft (1283.2 and 1281.6 m), a 4217 ft (1285.7 m) level was reached after 400 yr B.P. This level lowered to 4214 ft (1284.4 m) in the mid to late 1700 s A.D. The lake levels have since stabilized aroung a 4200 ft (1280 m) mean.

Murchison, Stuart B.↗